JP3080441B2 - Paste nickel electrode and alkaline storage battery - Google Patents
Paste nickel electrode and alkaline storage batteryInfo
- Publication number
- JP3080441B2 JP3080441B2 JP03187097A JP18709791A JP3080441B2 JP 3080441 B2 JP3080441 B2 JP 3080441B2 JP 03187097 A JP03187097 A JP 03187097A JP 18709791 A JP18709791 A JP 18709791A JP 3080441 B2 JP3080441 B2 JP 3080441B2
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- paste
- nickel hydroxide
- eutectic
- storage 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.)
- Expired - Lifetime
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 89
- 229910052759 nickel Inorganic materials 0.000 title claims description 41
- 238000003860 storage Methods 0.000 title claims description 16
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 38
- 239000011149 active material Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 18
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 17
- 230000005496 eutectics Effects 0.000 claims description 16
- 238000002441 X-ray diffraction Methods 0.000 claims description 15
- 239000010941 cobalt Substances 0.000 claims description 13
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
- 229910052793 cadmium Inorganic materials 0.000 claims description 9
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 9
- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 description 16
- 229910006279 γ-NiOOH Inorganic materials 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000005245 sintering Methods 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 229910002640 NiOOH Inorganic materials 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910003160 β-NiOOH Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000000615 nonconductor Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- Battery Electrode And Active Subsutance (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ペースト式ニッケル極
およびこのペースト式ニッケル極とカドミウム、亜鉛ま
たは水素吸蔵合金等を含む負極とを備えたアルカリ蓄電
池に関するものである。The present invention relates to a paste-type nickel electrode
And this paste nickel electrode with cadmium, zinc or
Or an alkaline storage device equipped with a negative electrode containing a hydrogen storage alloy or the like
It is about a pond .
【０００２】[0002]
【従来の技術】従来アルカリ蓄電池用ニッケル極として
は、例えばカーボニルニッケルをパンチドメタル上に焼
結成形した基板に硝酸ニッケル等のニッケル塩を水溶液
の形で充填後、アルカリ液中で水酸化ニッケルに転化し
た、いわゆる焼結式が主流であった。焼結式の利点とし
て、基板であるカーボニルニッケルの焼結体が孔径数〜
１０μｍの非常に微細な細孔構造であるため、元来不導
体である水酸化ニッケルの集電能力に優れていることが
挙げられる。反面ニッケル極全体に占める基板体積の比
率が２０％程度必要であり、その分活物質の充填量が制
限されてしまい、ニッケル極としての容量密度が４５０
ｍＡｈ／ｃｃ程度しか得られないという欠点があった。2. Description of the Related Art Conventionally, as a nickel electrode for an alkaline storage battery, for example, a nickel salt such as nickel nitrate is filled in a substrate formed by sintering carbonyl nickel on a punched metal in the form of an aqueous solution and then nickel hydroxide in an alkaline solution. The so-called sintering method was mainly used. The advantage of the sintering method is that the sintered body of carbonyl nickel as the substrate has a pore size of ~
Due to the very fine pore structure of 10 μm, it is mentioned that nickel hydroxide, which is originally a non-conductor, has excellent current collecting ability. On the other hand, the ratio of the substrate volume to the entire nickel electrode is required to be about 20%, and the amount of the active material to be filled is limited.
There is a drawback that only about mAh / cc can be obtained.
【０００３】これらの欠点を改良する試みとして、ペー
スト式ニッケル極が提案されている。ペースト式ニッケ
ル極は孔径１００〜５００μｍのスポンジ状あるいはフ
ェルト状金属多孔体を基板とし、この基板の孔に粉末状
水酸化ニッケルを適当な溶媒やバインダーでペースト状
に調製したものを充填し、乾燥、加圧して得られるもの
である。また、ニッケル極全体に占める基板の体積比率
を１０％未満に低下させることができるため、活物質の
充填量を増加することが可能となり、同容量密度に換算
すると６００ｍＡｈ／ｃｃ程度まで向上することができ
る。このペースト式ニッケル極に使用される前記粉末状
水酸化ニッケルは原理的には焼結式と同様に硝酸ニッケ
ル、硫酸ニッケル等のニッケル塩の水溶液を過剰の苛性
ソーダや苛性カリ等のアルカリ水溶液と、直径１〜数１
０ミクロンの粒子を生成させるように反応させ、沈澱物
を水洗、乾燥して得られるものが一般的である。[0003] As an attempt to improve these disadvantages, a paste-type nickel electrode has been proposed. The paste-type nickel electrode has a sponge-like or felt-like porous metal body having a pore diameter of 100 to 500 μm as a substrate, and the pores of the substrate are filled with powdered nickel hydroxide prepared into a paste with an appropriate solvent or binder and dried. , Obtained by pressing. In addition, since the volume ratio of the substrate to the entire nickel electrode can be reduced to less than 10%, the amount of the active material to be filled can be increased, and the equivalent capacity density can be improved to about 600 mAh / cc. Can be. The powdered nickel hydroxide used for this paste-type nickel electrode is, in principle, an aqueous solution of a nickel salt such as nickel nitrate or nickel sulfate and an aqueous solution of an alkali such as caustic soda or caustic potash in the same manner as in the sintering method. 1 to number 1
The reaction is generally carried out so as to form 0-micron particles, and the precipitate is generally washed with water and dried to obtain a precipitate.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、前記方
法にて作製したペースト式ニッケル極には数々の問題点
が存在する。とりわけ、充放電を行った際の水酸化ニッ
ケルの利用率が小さいという問題、充放電サイクルによ
る活物質の膨潤が著しく顕著なものである問題が挙げら
れる。このような問題を生ずる原因として基板の集電性
能の差が挙げられる。前記の通り焼結式基板の孔径が数
〜１０μｍであるのに対し、ペースト式の基板であるス
ポンジ状及びフェルト状金属多孔体は１００〜５００μ
ｍと数十倍も大きい。すなわち反応の際の活物質中の電
荷移動距離が長くなってしまい、抵抗による分極が大き
くなる傾向にある。分極の大きい電極における欠点とし
て放電電圧の低下ならびに充電中に不可逆な充電生成物
を生ずることが挙げられる。この不可逆な充電生成物は
一般にγ−ＮｉＯＯＨとして知られており、正常なニッ
ケル極の充電生成物であるβ−ＮｉＯＯＨと比較して放
電されにくく、また結晶がＣ軸方向に伸びた形態のため
活物質の膨潤を生じ易いことが知られている。すなわち
焼結方式とペースト方式を比較すると水酸化ニッケルと
して同じものを使用した場合、基板の集電能力の違いに
起因してペースト方式は利用率低下や活物質の膨潤をお
こし易い欠点があり、その原因は不可逆な充電生成物で
あるγ−ＮｉＯＯＨの生成が大きく関与していると言う
ことができる。However, there are many problems in the paste-type nickel electrode manufactured by the above method. In particular, there is a problem that the utilization rate of nickel hydroxide during charge / discharge is small, and a problem that the swelling of the active material due to the charge / discharge cycle is remarkable. The cause of such a problem is a difference in current collecting performance of the substrates. As described above, the pore diameter of the sintered substrate is several to 10 μm, whereas the sponge-like and felt-like porous metal bodies that are the paste-type substrates are 100 to 500 μm.
m and several tens of times larger. That is, the charge transfer distance in the active material at the time of the reaction becomes long, and polarization due to resistance tends to increase. Disadvantages of highly polarized electrodes include reduced discharge voltage and the formation of irreversible charge products during charging. This irreversible charge product is generally known as γ-NiOOH, is less likely to be discharged compared to β-NiOOH which is a normal nickel electrode charge product, and has a form in which the crystal extends in the C-axis direction. It is known that swelling of an active material is likely to occur. That is, when the same method is used as the nickel hydroxide when comparing the sintering method and the paste method, the paste method has a drawback that the utilization rate decreases and the active material tends to swell due to the difference in current collecting ability of the substrate, It can be said that the cause is largely related to the generation of γ-NiOOH which is an irreversible charge product.
【０００５】この問題に対する対策として、焼結式にお
いても広く知られていたコバルト化合物の添加をペース
ト方式に、例えば特公昭５７−５３４４、特開昭５３−
５１４４９号公開公報に示される様に金属コバルト、特
開昭６１−１３８４５８に示される様に一酸化コバルト
といった導電性に優れた形態のコバルトを配合すること
で、分極を抑制する試みが広く行われている。また特開
平１−２６０７６２、特開平２−３００６１に示される
様に水酸化ニッケルの結晶中にカドミウムまたは亜鉛等
を共晶状態にして添加する試みも同様に行われている。
しかしながら何れの方法も上記問題に対して充分な対策
とは言えず、例えば利用率に関しても焼結式が９５％以
上であるのに対しペースト式では９０％前後が限界であ
り、サイクル寿命に関しても焼結式が５００サイクル以
上であるのに対しペースト式が３００サイクル前後と劣
っているのが現状で、これらの問題がペースト式ニッケ
ル極の普及を妨げる大きな障害となっていた。[0005] As a countermeasure to this problem, the paste method the addition of the cobalt compound which has been widely known in the sintered, for example, Japanese Patent Publication 57-5344, JP-Open Sho 53-
Attempts have been widely made to suppress polarization by blending cobalt having excellent conductivity, such as cobalt metal as disclosed in JP-A- 51449, and cobalt monoxide as disclosed in JP-A-61-138458. ing. Also, as shown in JP-A-1-260762 and JP-A-2-30061, attempts to add cadmium, zinc, or the like to crystals of nickel hydroxide in a eutectic state have been made.
However, none of these methods can be said to be a sufficient measure against the above problems. For example, the sintering method has a utilization factor of 95% or more, while the paste method has a limit of about 90%. At present, the sintering method is inferior to about 300 cycles while the sintering method is 500 cycles or more, and these problems have been a major obstacle to the spread of the paste-type nickel electrode.
【０００６】本発明は、前記従来の問題を解決するため
になされたもので、高利用率でかつ長寿命のペースト式
ニッケル極を提供しようとするものである。本発明は、
利用率が高いペースト式ニッケル極を備えた長寿命なア
ルカリ蓄電池を提供しようとするものである。 The present invention has been made to solve the above-mentioned conventional problems, and an object of the present invention is to provide a paste-type nickel electrode having a high utilization factor and a long life. The present invention
A long-life electrode with a highly-utilized paste-type nickel electrode
It is intended to provide a Lucari storage battery.
【０００７】[0007]
【課題を解決するための手段】本発明に係るペースト式
ニッケル極は、水酸化ニッケル（Ｎｉ（ＯＨ）2）を主
体とする活物質と、前記水酸化ニッケルと共晶していな
い金属コバルトもしくはコバルト酸化物とを含むペース
トを金属多孔体を有する基板に充填してなるペースト式
ニッケル極において、前記水酸化ニッケルは、ＣｕＫα
線を用いるＸ線回折における（１０１）面のピークの半
価幅が０．８゜／２θ以上であることを特徴とするもの
である。本発明に係るペースト式ニッケル極は、水酸化
ニッケル（Ｎｉ（ＯＨ）2）を主体とする活物質と、前
記水酸化ニッケルと共晶していない金属コバルトもしく
はコバルト酸化物とを含むペーストを金属多孔体を有す
る基板に充填してなるペースト式ニッケル極において、
前記水酸化ニッケルは、ＣｕＫα線を用いるＸ線回折に
おける（１０１）面のピークの半価幅が０．８゜／２θ
以上であると共に、カドミウムもしくは亜鉛が共晶され
ていることを特徴とするものである。本発明に係わるア
ルカリ蓄電池は、水酸化ニッケル（Ｎｉ（ＯＨ）2）を
主体とする活物質と、前記水酸化ニッケルと共晶してい
ない金属コバルトもしくはコバルト酸化物とを含むペー
ストを金属多孔体を有する基板に充填してなるペースト
式ニッケル極を備えたアルカリ蓄電池において、前記水
酸化ニッケルは、ＣｕＫα線を用いるＸ線回折における
（１０１）面のピークの半価幅が０．８゜／２θ以上で
あることを特徴とするものである。本発明に係わるアル
カリ蓄電池は、水酸化ニッケル（Ｎｉ（ＯＨ）2）を主
体とする活物質と、前記水酸化ニッケルと共晶していな
い金属コバルトもしくはコバルト酸化物とを含むペース
トを金属多孔体を有する基板に充填してなるペースト式
ニッケル極を備えたアルカリ蓄電池において、前記水酸
化ニッケルは、ＣｕＫα線を用いるＸ線回折における
（１０１）面のピークの半価幅が０．８゜／２θ以上で
あると共に、カドミウムもしくは亜鉛が共晶されている
ことを特徴とするものである。According to the present invention, there is provided a paste-type nickel electrode, wherein an active material mainly composed of nickel hydroxide (Ni (OH) 2 ) is not eutectic with the nickel hydroxide.
In a paste-type nickel electrode obtained by filling a substrate having a porous metal body with a paste containing metallic cobalt or cobalt oxide, the nickel hydroxide is CuKα
The half width of the peak on the (101) plane in X-ray diffraction using X-rays is 0.8 ゜ / 2θ or more. Paste-type nickel electrode according to the present invention, an active material composed mainly of nickel hydroxide (Ni (OH) 2), before
Cobalt metal not eutectic with nickel hydroxide
Is a paste-type nickel electrode obtained by filling a substrate having a porous metal body with a paste containing cobalt oxide ,
The nickel hydroxide has a half-value width of a peak of the (101) plane in X-ray diffraction using CuKα ray of 0.8 ° / 2θ.
In addition to the above, cadmium or zinc is eutectic. The alkaline storage battery according to the present invention comprises an active material mainly composed of nickel hydroxide (Ni (OH) 2 ) and a eutectic crystal of the nickel hydroxide.
In an alkaline storage battery provided with a paste-type nickel electrode in which a paste containing no metallic cobalt or cobalt oxide is filled in a substrate having a porous metal body, the nickel hydroxide is (101) in X-ray diffraction using CuKα radiation. ) The peak half-value width of the plane is 0.8 ° / 2θ or more. The alkaline storage battery according to the present invention is characterized in that an active material mainly composed of nickel hydroxide (Ni (OH) 2 ) is not eutectic with the nickel hydroxide.
In an alkaline storage battery provided with a paste-type nickel electrode obtained by filling a substrate having a porous metal body with a paste containing a metal cobalt or a cobalt oxide, the nickel hydroxide is formed by (101) X-ray diffraction using CuKα radiation. ) The peak half-width of the plane is 0.8 ° / 2θ or more, and cadmium or zinc is eutectic.
【０００８】前記金属多孔体としては、例えば、スポン
ジ状ニッケルやフェルト状ニッケルのような三次元構造
を有するものを挙げることができる。前記水酸化ニッケ
ルの製造方法としては硝酸ニッケルや硫酸ニッケル等の
ニッケル塩の水溶液と苛性ソーダや苛性カリ等のアルカ
リ水溶液との中和反応で得られるが、反応雰囲気のｐＨ
を調節することにより、同じ水酸化ニッケルでもＸ線回
折における（１０１）面のピークの半価幅の異なる結晶
を得ることができる。[0008] As the metal porous body, for example, a three-dimensional structure such as sponge-like nickel or felt-like nickel is used.
Mention may be made of those having a. The method for producing the nickel hydroxide is obtained by a neutralization reaction between an aqueous solution of a nickel salt such as nickel nitrate or nickel sulfate and an aqueous alkali solution such as caustic soda or potassium hydroxide.
By adjusting the value of, it is possible to obtain crystals having the same half-width of the peak of the (101) plane in X-ray diffraction even with the same nickel hydroxide.
【０００９】さらに水酸化ニッケルにカドミウム、亜鉛
から選択された金属元素を共晶状態で添加、および金属
コバルト、コバルト酸化物（例えば、一酸化コバルト、
水酸化コバルト）を添加することにより性能が向上す
る。Further, a metal element selected from cadmium and zinc is added to nickel hydroxide in a eutectic state, and metal cobalt and cobalt oxide (for example, cobalt monoxide,
The performance is improved by adding ( cobalt hydroxide) .
【００１０】[0010]
【作用】同じ水酸化ニッケルＮｉ（ＯＨ）２であっても
結晶性の大小により、γ−ＮｉＯＯＨの生成度合いが異
なる傾向にある。それは充電時の反応でＮｉ（ＯＨ）２
結晶は電解液界面のプロトン移動の自由度が結晶化の大
小により異なり、結晶性の小さいものの方がプロトン移
動の自由度は高い傾向にあり、反面プロトン移動の不自
由なものほどγ−ＮｉＯＯＨを生成しやすい傾向にある
ことから、全体的には結晶性の大きなＮｉ（ＯＨ）２は
γ−ＮｉＯＯＨを生成しやすいと言うことができる。The degree of formation of γ-NiOOH tends to differ depending on the crystallinity of the same nickel hydroxide Ni (OH) 2 . It is a reaction during charging, Ni (OH) 2
In crystals, the degree of freedom of proton transfer at the electrolyte interface varies depending on the degree of crystallization, and those with low crystallinity tend to have higher degrees of freedom of proton transfer, while those with less proton transfer have higher γ-NiOOH. It can be said that Ni (OH) 2 having high crystallinity as a whole is easy to generate γ-NiOOH because it tends to be easily generated.
【００１１】Ｎｉ（ＯＨ）2 の結晶性を示す尺度として
は数々の方法があるが、発明者は特にＸ線回折を行った
際の（１０１）面、Ｃｕ Ｋα管球を使用した場合２θ
値で３８．７°付近に見られるピークの半価幅との間に
高い相関性を見いだして本発明を作成した。充電時のβ
−ＮｉＯＯＨ＋γ−ＮｉＯＯＨ量に対するγ一Ｎｉ００
Ｈの比率が小さいほど、ニッケル極の利用率は高く、ま
た活物質の膨潤度合いが小さいため、サイクル寿命が大
きい傾向にある。Although there are various methods for measuring the crystallinity of Ni (OH) 2 , the inventors have found that the X-ray diffraction (101) plane, especially when a Cu Kα tube is used, is 2θ.
The present invention was found by finding a high correlation between the peak value and the half width at around 38.7 ° . At the time of charging β
−NiOOH + γ−NiOOH with respect to the amount of NiOOH
As the ratio of H is smaller, the utilization rate of the nickel electrode is higher, and the degree of swelling of the active material is smaller, so that the cycle life tends to be longer.
【００１２】[0012]
【実施例】以上本発明の効果を実施例により詳細に説明
する。まず主活物質である水酸化ニッケルを下記の方法
で調製した。反応雰囲気のｐＨが一定に管理された環境
下で硫酸ニッケル水溶液と苛性ソーダ水溶液を順次投入
し、結晶成長、水洗、乾燥を経て、粒径１〜３０μｍの
水酸化ニッケルを作製した。反応雰囲気のｐＨ値を４種
類にさせることにより結晶性の異なるＮｉ（ＯＨ）２を
４種類得ることができた。EXAMPLES The effects of the present invention will be described in detail with reference to examples. First, nickel hydroxide as a main active material was prepared by the following method. An aqueous solution of nickel sulfate and an aqueous solution of caustic soda were sequentially added under an environment in which the pH of the reaction atmosphere was controlled to be constant, and crystal growth, washing with water, and drying were performed to produce nickel hydroxide having a particle size of 1 to 30 μm. By changing the pH value of the reaction atmosphere to four types, four types of Ni (OH) 2 having different crystallinities could be obtained.
【００１３】この水酸化ニッケルを島津製作所（株）製
ＸＤ−３４型Ｘ線回折分析装置にＣｕ Ｋα管球および
グラフィトモノクロメータを装着して結晶性を測定した
ところ、（１０１）面を示す３８．７°付近のピークの
半価幅が０．９、０．８、０．７、０．６°に相当する
チャートを示した。チャートの一例を図１に示す。この
水酸化ニッケル１００重量部に対して一酸化コバルト１
０重量部、カルボキシメチルセルロース０．３重量部を
水３０重量部と共に混練してペースト状に調製後、この
ペーストを孔径３００μｍのスポンジ状ニッケル多孔体
に充填し、乾燥、加圧、リード溶接を経て、本発明のペ
ースト式ニッケル極を作製した。The crystallinity of the nickel hydroxide was measured by mounting a Cu Kα tube and a graphite monochromator on an XD-34 type X-ray diffraction analyzer manufactured by Shimadzu Corporation. The chart shows that the half width of the peak near 38.7 ° corresponds to 0.9, 0.8, 0.7, and 0.6 °. One example of the chart is shown in FIG. Cobalt monoxide 1 per 100 parts by weight of this nickel hydroxide
0 parts by weight and 0.3 parts by weight of carboxymethylcellulose are kneaded with 30 parts by weight of water to prepare a paste, and then the paste is filled into a sponge-like nickel porous body having a pore diameter of 300 μm, dried, pressurized, and subjected to lead welding. The paste type nickel electrode of the present invention was produced.
【００１４】このペースト式ニッケル極をペースト式カ
ドミウム極、ナイロン製セパレータと共に捲回して電池
缶に挿入し、ＡＡサイズのニッケルカドミウム蓄電池を
作製し、０．３Ｃ充電／１Ｃ充電の充放電サイクルを５
００サイクル行った。その時のサイクル数に対するニッ
ケル極理論容量に対する利用率の推多を図２に示す。This paste-type nickel electrode is wound together with a paste-type cadmium electrode and a nylon separator and inserted into a battery can to produce an AA-size nickel-cadmium storage battery, and a charge / discharge cycle of 0.3 C charge / 1 C charge is performed.
00 cycles were performed. FIG. 2 shows the estimation of the utilization factor with respect to the theoretical capacity of the nickel electrode with respect to the cycle number at that time.
【００１５】次に５００サイクル終了後の電池を充電状
態で分解し、ニッケル極を取り出し粉砕処理して同様に
Ｘ線回折分析を行い、２θで１３°付近に見られるγ−
ＮｉＯＯＨのピーク高さ（Ｐ−γ）と、１９°付近にみ
られるβ−ＮｉＯＯＨのピーク（Ｐ−β）を測定し、
（Ｐ−γ）／（Ｐ−γ）＋（Ｐ−β））の値から全体中
のγ−ＮｉＯＯＨの比率を算出した。上記半値幅に対す
るγ−ＮｉＯＯＨの比率を図３に示す。Next, after 500 cycles, the battery is disassembled in a charged state, the nickel electrode is taken out and pulverized, and subjected to X-ray diffraction analysis in the same manner.
The peak height (P-γ) of NiOOH and the peak (P-β) of β-NiOOH observed around 19 ° were measured.
From the value of (P-γ) / (P-γ) + (P-β)), the ratio of γ-NiOOH in the whole was calculated. FIG. 3 shows the ratio of γ-NiOOH to the half width.
【００１６】図２によると、（１０１）面ピークの半価
幅が０．９、０．８°の水酸化ニッケルを使用したニッ
ケル極の場合、利用率が９５％と高く、かつ５００サイ
クルを経ても利用率の変化がほとんど見られない。図３
のγ−ＮｉＯＯＨ比率も２０％未満と小さい傾向にあ
る。これに対し、０．７、０．６°のものは利用率が最
高でも９０％であり、しかもサイクル中の低下が著しく
３００サイクル付近で初期の５０％未満に低下してい
る。これに対応してγ−ＮｉＯＯＨ比率は４０％〜８０
％と非常に高い傾向にあり、活物質膨潤による電解液の
偏在を起こしていた。According to FIG. 2, in the case of a nickel electrode using nickel hydroxide having a (101) plane peak having a half width of 0.9 and 0.8 °, the utilization factor is as high as 95% and 500 cycles are required. Almost no change in usage rate is seen even after passing through. FIG.
Also tend to be as small as less than 20%. On the other hand, those with 0.7 and 0.6 ° have the maximum utilization rate of 90%, and the decrease during the cycle is remarkable, dropping to less than the initial 50% around 300 cycles. Correspondingly, the γ-NiOOH ratio is between 40% and 80%.
%, Which is very high, and uneven distribution of the electrolytic solution was caused by swelling of the active material.
【００１７】本実施例はコバルト系の添加剤として−酸
化コバルトを使用したが、代用として金属コバルトや水
酸化コバルト等のコバルト酸化物を使用しても同様な効
果が得られる。またここでは詳細な結果を示さないが、
水酸化ニッケルにカドミウムまたは亜鉛を３〜７重量％
共晶添加したペースト式ニッケル極においては７００サ
イクルの経過後も利用率の変化は見られず、良好な特性
を示した。In this embodiment, cobalt oxide is used as a cobalt-based additive. However, similar effects can be obtained by using a cobalt oxide such as metal cobalt or cobalt hydroxide instead. I will not show detailed results here,
3-7% by weight of cadmium or zinc in nickel hydroxide
The eutectic-added paste-type nickel electrode did not show any change in utilization even after 700 cycles, and exhibited good characteristics.
【００１８】[0018]
【発明の効果】以上詳述したように本発明によれば、水
酸化ニッケルの利用率が高く、かつ長寿命なペースト式
ニッケル極およびかかるペースト式ニッケル極を備えた
アルカリ蓄電池を提供することができ、その工業的価値
は大である。As described in detail above, according to the present invention, the utilization of nickel hydroxide is high , and the paste
With nickel electrode and such paste-type nickel electrode
An alkaline storage battery can be provided , and its industrial value is great.
【図１】水酸化ニッケルのＸ線回折分析のチャート図で
ある。FIG. 1 is a chart of an X-ray diffraction analysis of nickel hydroxide.
【図２】本発明のニッケル極を使用した電池の充放電サ
イクルとニッケル極の活物質の利用率との関係図であ
る。FIG. 2 is a graph showing the relationship between the charge / discharge cycle of a battery using a nickel electrode of the present invention and the utilization rate of an active material of the nickel electrode.
【図３】水酸化ニッケルの半価幅と５００サイクル後の
γ−ＮｉＯＯＨの生成比率とを示した図である。FIG. 3 is a diagram showing the half width of nickel hydroxide and the production ratio of γ-NiOOH after 500 cycles.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 寺岡 浩仁 東京都品川区南品川三丁目４番10号 東 芝電池株式会社内 (72)発明者 秦 勝幸 東京都品川区南品川三丁目４番10号 東 芝電池株式会社内 (56)参考文献 特開 昭63−152866（ＪＰ，Ａ) 特開 平１−260762（ＪＰ，Ａ) 特開 平２−30061（ＪＰ，Ａ) 特公 昭54−3836（ＪＰ，Ｂ２) ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hirohito Teraoka 3- 4-10 Minamishinagawa, Shinagawa-ku, Tokyo Inside Toshiba Battery Corporation (72) Inventor Katsuyuki Hata 3-4-1 Minamishinagawa, Shinagawa-ku, Tokyo No. Toshiba Battery Corporation (56) References JP-A-63-152866 (JP, A) JP-A-1-260762 (JP, A) JP-A-2-30061 (JP, A) 3836 (JP, B2)
Claims (6)
体とする活物質と、前記水酸化ニッケルと共晶していな
い金属コバルトもしくはコバルト酸化物とを含むペース
トを金属多孔体を有する基板に充填してなるペースト式
ニッケル極において、 前記水酸化ニッケルは、ＣｕＫα線を用いるＸ線回折に
おける（１０１）面のピークの半価幅が０．８゜／２θ
以上であることを特徴とするペースト式ニッケル極。1. An active material mainly composed of nickel hydroxide (Ni (OH) 2 ), which is not eutectic with the nickel hydroxide.
In a paste-type nickel electrode obtained by filling a substrate having a porous metal body with a paste containing metallic cobalt or a cobalt oxide, the nickel hydroxide has a peak of (101) plane in X-ray diffraction using CuKα ray . Half width is 0.8 ゜ / 2θ
A paste-type nickel electrode characterized by the above.
体とする活物質と、前記水酸化ニッケルと共晶していな
い金属コバルトもしくはコバルト酸化物とを含むペース
トを金属多孔体を有する基板に充填してなるペースト式
ニッケル極において、 前記水酸化ニッケルは、ＣｕＫα線を用いるＸ線回折に
おける（１０１）面のピークの半価幅が０．８゜／２θ
以上であると共に、カドミウムもしくは亜鉛が共晶され
ていることを特徴とするペースト式ニッケル極。 2. Nickel hydroxide (Ni (OH) 2 )
The active material is not eutectic with the nickel hydroxide.
Pace containing metallic cobalt or cobalt oxide
Paste type in which the substrate is filled with a metal porous body
At the nickel electrode, the nickel hydroxide is subjected to X-ray diffraction using CuKα radiation.
The half width of the peak of the (101) plane is 0.8 ゜ / 2θ
In addition, cadmium or zinc is eutectic
A paste nickel electrode.
いるＸ線回折における（１０１）面のピークの半価幅が
０．８゜／２θ以上であると共に、亜鉛が共晶されてい
ることを特徴とする請求項２記載のペースト式ニッケル
極。 3. The nickel hydroxide uses CuKα radiation.
The half-value width of the (101) plane peak in X-ray diffraction
0.8 ゜ / 2θ or more and zinc is eutectic
3. The paste-type nickel according to claim 2, wherein
very.
体とする活物質と、前記水酸化ニッケルと共晶していな
い金属コバルトもしくはコバルト酸化物とを含むペース
トを金属多孔体を有する基板に充填してなるペースト式
ニッケル極を備えたアルカリ蓄電池において、 前記水酸化ニッケルは、ＣｕＫα線を用いるＸ線回折に
おける（１０１）面のピークの半価幅が０．８゜／２θ
以上であることを特徴とするアルカリ蓄電池。4. An active material containing nickel hydroxide (Ni (OH) 2 ) as a main component and not eutectic with the nickel hydroxide.
In an alkaline storage battery provided with a paste-type nickel electrode obtained by filling a substrate having a porous metal body with a paste containing metallic cobalt or a cobalt oxide, the nickel hydroxide is obtained by X-ray diffraction using CuKα ray (101 ) The half width of the peak of the plane is 0.8 ゜ / 2θ
An alkaline storage battery as described above.
体とする活物質と、前記水酸化ニッケルと共晶していな
い金属コバルトもしくはコバルト酸化物とを含むペース
トを金属多孔体を有する基板に充填してなるペースト式
ニッケル極を備えたアルカリ蓄電池において、 前記水酸化ニッケルは、ＣｕＫα線を用いるＸ線回折に
おける（１０１）面の ピークの半価幅が０．８゜／２θ
以上であると共に、カドミウムもしくは亜鉛が共晶され
ていることを特徴とするアルカリ蓄電池。 5. Nickel hydroxide (Ni (OH) 2 )
The active material is not eutectic with the nickel hydroxide.
Pace containing metallic cobalt or cobalt oxide
Paste type in which the substrate is filled with a metal porous body
In an alkaline storage battery provided with a nickel electrode, the nickel hydroxide is subjected to X-ray diffraction using CuKα radiation.
The half width of the peak of the (101) plane is 0.8 ゜ / 2θ
In addition, cadmium or zinc is eutectic
An alkaline storage battery characterized in that:
いるＸ線回折における（１０１）面のピークの半価幅が
０．８゜／２θ以上であると共に、亜鉛が共晶されてい
ることを特徴とする請求項５記載のアルカリ蓄電池。 6. The nickel hydroxide uses CuKα radiation.
The half-value width of the (101) plane peak in X-ray diffraction
0.8 ゜ / 2θ or more and zinc is eutectic
The alkaline storage battery according to claim 5, wherein
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03187097A JP3080441B2 (en) | 1991-04-25 | 1991-04-25 | Paste nickel electrode and alkaline storage battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03187097A JP3080441B2 (en) | 1991-04-25 | 1991-04-25 | Paste nickel electrode and alkaline storage battery |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10018738A Division JP3094062B2 (en) | 1998-01-30 | 1998-01-30 | Method for producing paste-type nickel electrode and method for producing alkaline storage battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04328257A JPH04328257A (en) | 1992-11-17 |
| JP3080441B2 true JP3080441B2 (en) | 2000-08-28 |
Family
ID=16200056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03187097A Expired - Lifetime JP3080441B2 (en) | 1991-04-25 | 1991-04-25 | Paste nickel electrode and alkaline storage battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3080441B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3151340B2 (en) * | 1993-08-19 | 2001-04-03 | 東芝電池株式会社 | Alkaline storage battery |
| JP2802482B2 (en) | 1994-10-28 | 1998-09-24 | 古河電池株式会社 | Nickel electrode for alkaline secondary batteries |
| FR2731297B1 (en) * | 1995-03-03 | 1997-04-04 | Accumulateurs Fixes | NICKEL ELECTRODE FOR ALKALINE BATTERY |
| JP5868669B2 (en) * | 2010-11-30 | 2016-02-24 | 三洋電機株式会社 | Alkaline storage battery |
| JP6142295B1 (en) | 2016-06-07 | 2017-06-07 | 株式会社田中化学研究所 | Positive electrode active material for secondary battery |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63152866A (en) * | 1986-12-16 | 1988-06-25 | Yuasa Battery Co Ltd | Nickel active material for storage battery and its manufacture |
| JPH0724218B2 (en) * | 1988-04-11 | 1995-03-15 | 株式会社ユアサコーポレーション | Nickel electrode for alkaline battery and battery using the same |
| JPH0777129B2 (en) * | 1988-07-19 | 1995-08-16 | 株式会社ユアサコーポレーション | Nickel electrode active material and method for producing the same, nickel electrode and method for producing alkaline battery using the same |
-
1991
- 1991-04-25 JP JP03187097A patent/JP3080441B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04328257A (en) | 1992-11-17 |
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