JPS5990357A - Positive plate for alkaline battery - Google Patents
Positive plate for alkaline batteryInfo
- Publication number
- JPS5990357A JPS5990357A JP57199973A JP19997382A JPS5990357A JP S5990357 A JPS5990357 A JP S5990357A JP 57199973 A JP57199973 A JP 57199973A JP 19997382 A JP19997382 A JP 19997382A JP S5990357 A JPS5990357 A JP S5990357A
- Authority
- JP
- Japan
- Prior art keywords
- nickel
- pasted
- sponge
- glycol
- electrode plate
- 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
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
-
- 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
Abstract
Description
【発明の詳細な説明】
本発明は、スポンジ状ニッ））ル多孔体にペース１〜状
の活物質を充填するアルカリ電池用正極板に関Ｊるもの
で、活物質粉末をペース１〜化する際に有機溶媒、例え
ばエチレングリコール、プロピレングリコールあるいは
１へり■チ１ノングリ］−ル等の単体もしくはそれらの
混合物を用いることにより放電性能のすぐれた正極板を
得ることを目的とづるーｂのである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a positive electrode plate for alkaline batteries in which a sponge-like porous body is filled with an active material in the form of paste 1. The purpose of this method is to obtain a positive electrode plate with excellent discharge performance by using an organic solvent such as ethylene glycol, propylene glycol, or a mixture thereof, such as ethylene glycol, propylene glycol, or a mixture thereof. be.
従来、アルカリ電池の正極板の基板どしては、ニッケル
粉末の焼結体が用いられているが、その多孔磨は７０〜
８０％程度であり、これ以１に多孔洟を上げると、その
機械的強度が著しく減少し、したがってぞの空隙内に正
極活物質を充填した場合に、基板の変形、亀裂や活物質
の剥離等をＩＲ来する欠点があった。また、活物質を充
填Ｍる場合、通常減圧含浸法どよばれる方法すなわち硝
酸ニッケルや硫酸ニッノノル等の塩の水溶液を基板に減
圧含浸したのち、アルカリ水溶液で処理し、さらに湯洗
、乾燥Ｊるという操作を繰り返す方法がとられている。Conventionally, a sintered body of nickel powder has been used as a substrate for the positive electrode plate of alkaline batteries, but the porosity of the sintered body is 70~
This is approximately 80%, and increasing the porosity beyond this level will significantly reduce its mechanical strength, and therefore, when the positive electrode active material is filled into the voids, the substrate may deform, crack, or the active material may peel off. There was a drawback that IR was generated. In addition, when filling the active material, a method called vacuum impregnation method is usually used, that is, the substrate is impregnated with an aqueous solution of a salt such as nickel nitrate or ninonol sulfate under reduced pressure, and then treated with an alkaline aqueous solution, followed by washing with hot water and drying. A method of repeating this operation is used.
しかしながら、−回の操作によって充填される量は少り
、シかも、２回目から充填される量は次第に減少してく
るので通常４〜１０回の操作を繰り返り必要がある。そ
のため製造工程が複雑で経済的コストが高くなるという
欠点があった。However, the amount filled in the first operation is small, and the amount filled from the second time onward gradually decreases, so it is usually necessary to repeat the operation 4 to 10 times. Therefore, the manufacturing process is complicated and the economic cost is high.
一方、エチレングリコールやプロピレングリ三］−ル等
の（ｉｔ幾溶媒どフッ系ｔｒｉ ｌ１ｉｊの／） ｉＢ
！液とを用いて水酸化ニッケルとグラフアイ１−どの混
合物をペース１〜ｆｔ、 １．、、７こ後、ニッケル網
等の支持体に塗層する、いわゆるロールボンデツド方式
が提案されているが、この方法は製造■稈が簡便である
反面、極板の強度が小さいために寿命の点で問題がある
ことが知られている。On the other hand, ethylene glycol, propylene glycol, etc.
! Using a mixture of nickel hydroxide and Grapheye 1-ft, paste 1-ft. After that, the so-called roll bonding method was proposed, in which a layer is coated on a support such as a nickel net, but while this method is easy to manufacture, it has a short lifespan due to the low strength of the electrode plate. is known to have problems.
そこで近釘、三次元的に連続した４Ｍ ｉ’ｂを有Ｊる
ニッケル金属Ｊ、りなるスポンジ状多孔体にカルボ４シ
メヂルレル［１−ス等の水溶）（ｋでペース１−状にし
た正極）古物質を直接充ｌ眞するもの７ノ畳１目されて
さている。Therefore, a positive electrode was prepared using a nickel metal having three-dimensionally continuous 4M i'b, and a water-soluble carbonaceous material (such as a water-soluble carbonate such as 1-base) in a spongy porous material. ) There are seven tatami mats that are directly filled with ancient materials.
三次元的に連続したＤｊ迄を右するスポンジ状ニッケル
多孔体は、その多孔度が９０・−９８％と高く、しかＬ
）ｌ幾緘的強Ｙａが大きい。ぞのうλ、孔径が人きいの
でこの多孔体に活物質を充１眞１′ると正極板の高容量
化を図る事が出来ると共に充填が極めて簡便になり連続
工稈が可能で経済的にも右利と２７る。しかしながら多
孔体と活物質粒子どの間の接触状態（Ｊ必ずしし良θ１
ではなく、カルボ：１−ジメチルセル［］−ス等の絶縁
物が存在覆ること１ｂ、＋４Ｉ板を乾燥する際に多孔体
１５導電祠の表面が一部分酸化されて電気抵抗が増大Ｊ
ること等の原因にＪ、−）て充分な極板の性能が１ｑら
れないという欠点がある。The sponge-like porous nickel material that extends to the three-dimensionally continuous Dj has a high porosity of 90.-98%, and only L
)l The strength of Ya is large. Since the pore diameter is small, if this porous body is filled with an active material, it is possible to increase the capacity of the positive electrode plate, and filling is extremely simple, making continuous production possible and economical. There are also 27 people on the right. However, the contact state between the porous body and the active material particles (J is always good θ1
Instead, an insulating material such as carbo:1-dimethylcell[]-su is present. 1b, When drying the +4I plate, the surface of the porous body 15 is partially oxidized, increasing the electrical resistance.
There is a drawback that sufficient performance of the electrode plate cannot be obtained due to J, -).
本発明は、活物質をペース１へ化Ｊ−る際の練液として
右１幾溶媒、例えばＴヂレングリ−１−ル、プロピレン
グリー１−ルあるいはトリ丁ヂレンクリー］−ル等の単
体あるい（よそれらの混合物を用いると、極板の放電性
能が著しく白土することを見出したことに基づくもので
ある。The present invention uses solvents such as T-dilene glycol, propylene glycol, tri-dilene glycol, etc. alone or ( This is based on the discovery that when a mixture of these is used, the discharge performance of the electrode plate is significantly reduced.
以下、本発明の実施例ならびにイの効里を詳述Ｊ−る。Examples of the present invention and its effects will be described in detail below.
本発明に用いた正極板は次の様にして製作した。The positive electrode plate used in the present invention was manufactured as follows.
まず、水酸化ニッケル８５部とニッケル粉末１５部どの
混合粉末にＴヂレングリ１−ル等の有機溶媒を加えてペ
ースト状にした。つぎ′にこのペーストを平均孔径０
、３ ｍ ｍ 、多孔度９り％、厚さ １．２ｍｍの三
次元的に連続した構造を有するスポンジ状ニッケル多孔
体に充填し、１００℃で４時間乾燥した後、フッ素樹脂
の分散液を含浸１）、更に８０℃で１時間乾燥して７）
＋ ｒう５００１＜０ ／’の圧力で加圧して本発明に
Ｊ：る正極板をｌ［７１：：。イしてこの正極板１枚ど
対極どして焼結式カドミウム負極板２枚と、電解液どし
てＳ 、 Ｇ 、１，２！＋０ （２０℃） Ｋ （’
） ｌ−１水溶液とを用いて公称容部１．ＯＡｔ＋の本
発明によるグラフデッドタイプの電池をφ１１作し、０
．ＩＯＡで１６時間充電した後、１．ＯＣＡで酸化第二
水銀電極に対してＯ■まで放電して活物質利用率を求め
た。練液どじで用いる有機溶媒の種類を変えた場合の活
物質利用率の変化を第１図に示す。図からプロピレング
リコールやエチレングリコール等のような比較的粘度の
高い有機溶媒を用いた場合に活物質利用率の良いことが
判る。そこで粘度の影響を児るｌζめに代表例どして王
チルアルコールとプロピレングリコールとのｉｌＮ合物
を練液として用いた場合の混合溶媒の粘度ど活物質利用
率との関係を第２図に示す。図から混合溶媒の粘度が２
０ｃ、ｐ、以上の範囲において活物質利用率の真い事が
判る。また、エチレングリコール、トリエチレングリコ
ールやメ５−
チルアルコール等の混合物を用いても同（］２の結束が
得られる事を確認した。First, an organic solvent such as T-dilene glycol was added to a mixed powder of 85 parts of nickel hydroxide and 15 parts of nickel powder to form a paste. Next, apply this paste with an average pore size of 0.
, 3 mm, 9% porosity, and 1.2 mm thick sponge-like porous nickel material having a three-dimensionally continuous structure was filled with the material, and after drying at 100°C for 4 hours, the fluororesin dispersion was Impregnation 1), further drying at 80°C for 1 hour 7)
The positive electrode plate according to the present invention is pressurized with a pressure of 5001<0/'. Then, put one positive electrode plate, two sintered cadmium negative electrode plates, and electrolyte as the opposite electrode. S, G, 1, 2! +0 (20℃) K ('
) 1-1 aqueous solution to a nominal volume of 1. A graph dead type battery according to the present invention of OAt+ was made with a diameter of 11 mm.
．． After charging for 16 hours with IOA, 1. The active material utilization rate was determined by discharging to O■ against a mercuric oxide electrode using OCA. Figure 1 shows the change in the active material utilization rate when the type of organic solvent used in the mixing process was changed. From the figure, it can be seen that the active material utilization rate is good when an organic solvent with relatively high viscosity, such as propylene glycol or ethylene glycol, is used. Therefore, as a representative example of the influence of viscosity, Figure 2 shows the relationship between the viscosity of the mixed solvent and the active material utilization rate when an ilN compound of kingyl alcohol and propylene glycol is used as a working solution. Shown below. From the figure, the viscosity of the mixed solvent is 2
It can be seen that the active material utilization rate is true in the range of 0c, p or more. It was also confirmed that the same bonding properties (2) can be obtained using a mixture of ethylene glycol, triethylene glycol, methyl alcohol, and the like.
次に、練液どしてプロピレングリコ：１−ルを用いて製
作した本発明による正極板１枚と、従来から公知のペー
ス１〜式カドミウム負極板１枚どを一ノーイ［１ン不織
布のセパレータを介して渦巻状に巻き、電解液にＳ、
Ｇ、１．３００（２０℃）水酸化カリウム水溶液を用い
て公称容ｉ１２，４Ａｈの本発明による密閉形ニッケル
・カドミウム電池（Δ）を製作した。Next, one positive electrode plate according to the present invention manufactured using propylene glycol: Wrap it in a spiral shape through a separator, add S to the electrolyte,
A sealed nickel-cadmium battery (Δ) according to the present invention having a nominal capacity of i12.4Ah was fabricated using an aqueous potassium hydroxide solution at 1.300°C (20°C).
また比較のために練液として０．６ｗｔ％カルポキシメ
チルレル［１−ス水溶液を用いた正極板を用いて従来法
による電池（Ｂ）を製作した。これらの電池を２０℃、
０．ＩＯＡで１６時間充電した後、０８２Ｃ△でｉ
、ｏｙｌ：で放電した時の放電特性を第３図に示す。図
から、本発明による電池（△〉は従来法による電池（、
Ｂ）よりも放電電位特性および放電容量共に著しく優れ
ている事が判る。For comparison, a battery (B) was manufactured using a conventional method using a positive electrode plate containing a 0.6 wt % aqueous solution of carboxymethylrel[1-su] as a mixing solution. These batteries at 20℃,
0. After charging with IOA for 16 hours, i with 082C△
, oil: is shown in FIG. 3. From the figure, the battery according to the present invention (△〉) is the battery according to the conventional method (,
It can be seen that both discharge potential characteristics and discharge capacity are significantly superior to B).
何故、活物質をペース１〜化する際の練液として有機溶
媒を用いると利用率が著しく向−１ニするのかは定かで
ないが、次の様な理由によるものと考え−〇−
られる。即ち、カルボキシメチルｐル１］−ス等の結着
剤の水溶液を用いて活物質をペースト化した場合には、
１輌板内に絶縁性の結着剤が含まれるために内部抵抗が
大きくなると考えられる。まＩζ、ペースｈ ｉ）：活
物質を充填した極板を乾燥づる際に、導電材粒子や多孔
体の骨格の表面の一部が酸化されて電気抵抗が大きくな
ると考えられる。そのために極板全体の内部抵抗が大き
くなり放電性能が悪くなるものど考えられる。しかしな
がら、本発明によると、極板内に絶縁性の物質が含まれ
ることはなく、Ｊ：だ、導電材の表面等が酸化されるこ
とも少ないと考えられる。そのために従来法による正極
板と比較して放電＋１１能が著しく向上するものと考え
られる。Although it is not clear why the use of an organic solvent as a mixing solution when converting the active material into paste 1 improves the utilization rate by 1, it is thought to be due to the following reasons. That is, when the active material is made into a paste using an aqueous solution of a binder such as carboxymethyl p-su,
It is thought that the internal resistance increases because an insulating binder is contained in one plate. Iζ, pace h i): When drying the electrode plate filled with the active material, it is thought that part of the surface of the conductive material particles and the skeleton of the porous body is oxidized, increasing the electrical resistance. It is conceivable that this may increase the internal resistance of the entire electrode plate, resulting in poor discharge performance. However, according to the present invention, no insulating substance is contained in the electrode plate, and it is thought that the surface of the conductive material is less likely to be oxidized. Therefore, it is considered that the discharge ability is significantly improved by +11 compared to the positive electrode plate made by the conventional method.
以上の様に本発明によると、活物質をペース１〜化する
際の練液に有機溶媒を用いることによって正極板の放電
性能を著しく向上さμることができる。As described above, according to the present invention, the discharge performance of the positive electrode plate can be significantly improved by using an organic solvent in the mixing solution when the active material is made into a paste.
第１図Ｉ」練液として用いる有機溶媒の種類を変えた場
合の活物質利用率の変化を示しｌｃ図、第２図は混合触
媒の粘度と活物質利用率との関係を示した図、第３図は
本発明による電池（△）と従来の方法による電池（Ｂ）
の１ＣΔ放電特性の比較図である。
グ Ｚ 凶
粕 宸 ＜ ｔｏ ’ｃ ） （（：、 ｒ
）方 ３ 図
０ ／、 ６
２゜放 電 容 ｔ （ＡＩｄ）Figure 1 is a lc diagram showing the change in the active material utilization rate when the type of organic solvent used as a mixing solution is changed, and Figure 2 is a diagram showing the relationship between the viscosity of the mixed catalyst and the active material utilization rate. Figure 3 shows a battery according to the present invention (△) and a battery according to the conventional method (B).
FIG. 2 is a comparison diagram of 1CΔ discharge characteristics of FIG. gu Z 紕 宸 ＜ to 'c ) ((:, r
) Way 3 Figure 0 /, 6
2゜Discharge capacity t (AId)
Claims (1)
末を有機溶媒、例えばエチレングリコール。 プ１コピレンゲリコールあるいは１−リＪヂレングリコ
ール等の単体もしくはそれらの混合物を用いてペースト
状にしたものを用いて、三次元的に連続した構造を有Ｊ
るスポンジ状ニッケル多孔体に充ＩＲｉることを特徴ど
Ｊるアルｈり電池用正極板。 ２、上記有機溶媒の単体、ｂ ＋、 ＜はそれらの混合
物の粘度が２０ｃ、１０以上である特許請求の範囲第１
項記載のアルカリ電池用正極板。[Claims] 1. Nickel hydroxide and active material powder, mainly containing conductive material, in an organic solvent such as ethylene glycol. A paste with a three-dimensionally continuous structure is made by using a single substance such as 1-copyrene glycol or 1-diylene glycol or a mixture thereof.
A positive electrode plate for an aluminum battery, characterized by being filled with a sponge-like porous nickel material. 2. The viscosity of the simple substance of the organic solvent, b + , < is 20 c, 10 or more, as a mixture thereof. Claim 1
A positive electrode plate for alkaline batteries as described in .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57199973A JPS5990357A (en) | 1982-11-15 | 1982-11-15 | Positive plate for alkaline battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57199973A JPS5990357A (en) | 1982-11-15 | 1982-11-15 | Positive plate for alkaline battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5990357A true JPS5990357A (en) | 1984-05-24 |
Family
ID=16416662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57199973A Pending JPS5990357A (en) | 1982-11-15 | 1982-11-15 | Positive plate for alkaline battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5990357A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103415945A (en) * | 2011-02-28 | 2013-11-27 | 应用材料公司 | Manufacturing of high capacity prismatic lithium-ion alloy anodes |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56149768A (en) * | 1980-04-18 | 1981-11-19 | Yuasa Battery Co Ltd | Sealed nickel-cadmium storage battery |
-
1982
- 1982-11-15 JP JP57199973A patent/JPS5990357A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56149768A (en) * | 1980-04-18 | 1981-11-19 | Yuasa Battery Co Ltd | Sealed nickel-cadmium storage battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103415945A (en) * | 2011-02-28 | 2013-11-27 | 应用材料公司 | Manufacturing of high capacity prismatic lithium-ion alloy anodes |
| US9240585B2 (en) | 2011-02-28 | 2016-01-19 | Applied Materials, Inc. | Manufacturing of high capacity prismatic lithium-ion alloy anodes |
| US9583770B2 (en) | 2011-02-28 | 2017-02-28 | Applied Materials, Inc. | Manufacturing of high capacity prismatic lithium-ion alloy anodes |
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