JP5622996B2 - Alkaline battery and method for producing alkaline battery - Google Patents

Alkaline battery and method for producing alkaline battery Download PDF

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JP5622996B2
JP5622996B2 JP2006300645A JP2006300645A JP5622996B2 JP 5622996 B2 JP5622996 B2 JP 5622996B2 JP 2006300645 A JP2006300645 A JP 2006300645A JP 2006300645 A JP2006300645 A JP 2006300645A JP 5622996 B2 JP5622996 B2 JP 5622996B2
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alkaline battery
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秀典 都築
秀典 都築
武男 野上
武男 野上
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    • 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
    • H01M4/06—Electrodes for primary cells
    • 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
    • H01M4/06—Electrodes for primary cells
    • H01M4/08—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped electrodes

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Description

本発明は、二酸化マンガン及びオキシ水酸化ニッケルの少なくとも何れか一方の正極活物質を有する正極合剤を備えたアルカリ電池およびこのアルカリ電池の製造方法に関するものである。   The present invention relates to an alkaline battery including a positive electrode mixture having a positive electrode active material of at least one of manganese dioxide and nickel oxyhydroxide, and a method for producing the alkaline battery.

一般に、上記アルカリ電池は、図６に示すように、有底円筒状の正極缶１内の内周壁面に黒鉛からなる導電膜２が塗布され、この導電膜２に外周面が接するように円筒状の正極合剤３が圧入・装填されるとともに、上記正極合剤３の内に水酸化カリウム電解液が含浸された円筒状のセパレータ４が配設されている。そして、このセパレータ４内に負極剤５が充填されるとともに、この負極剤５内に集電棒６が挿入されており、正極缶１の上端開口部にガスケット１０を介して当該開口部を塞ぐ略円板状の負極端子板１１が設けられている。   In general, as shown in FIG. 6, the alkaline battery is formed such that a conductive film 2 made of graphite is applied to the inner peripheral wall surface of a bottomed cylindrical positive electrode can 1, and the outer peripheral surface is in contact with the conductive film 2. A cylindrical positive electrode mixture 3 impregnated with a potassium hydroxide electrolyte is disposed in the positive electrode mixture 3. The separator 4 is filled with the negative electrode agent 5, and the current collector rod 6 is inserted into the negative electrode agent 5, so that the upper end opening of the positive electrode can 1 is covered with the gasket 10 via the gasket 10. A disc-shaped negative electrode terminal plate 11 is provided.

そして、上記正極合剤３は、二酸化マンガン及び水酸化ニッケルの少なくとも何れか一方の正極活物質に黒鉛、正極バインダー並びに水酸化カリウム水溶液を加えて湿式混合し、顆粒状に粉砕した後に、プレス成形することによって円筒状に形成されている。この正極バインダーとしては、ポリエチレンなどの増粘効果の低いものが用いられている（例えば、特許文献１）。   The positive electrode mixture 3 is prepared by adding graphite, a positive electrode binder, and an aqueous potassium hydroxide solution to at least one of positive electrode active materials of manganese dioxide and nickel hydroxide, wet-mixing them, and pulverizing them into granules, followed by press molding. By doing so, it is formed in a cylindrical shape. As this positive electrode binder, the thing with a low thickening effect, such as polyethylene, is used (for example, patent document 1).

ところが、上記正極バインダーとして上記ポリエチレンのような増粘効果の低いものを多量に混合したアルカリ電池は、電池反応に直接寄与する正極活物質の充填量が減少してしまうという欠点があった（例えば、特許文献１）。そこで、正極バインダーの充填量を少なくしようとすると、上記正極合剤３に充分なコア強度が得られなくなり、この結果、正極缶１内に圧入する際に、正極合剤３に割れ等の破壊が生じ、この破壊部分が電極反応に寄与しなくなってしまう恐れがあった。   However, an alkaline battery in which a large amount of a low-viscosity effect such as polyethylene is mixed as the positive electrode binder has a drawback in that the amount of the positive electrode active material that directly contributes to the battery reaction is reduced (for example, Patent Document 1). Therefore, if it is attempted to reduce the filling amount of the positive electrode binder, sufficient core strength cannot be obtained in the positive electrode mixture 3, and as a result, when the positive electrode can 1 is press-fitted into the positive electrode can 1, breakage or the like is broken. As a result, there is a fear that the destroyed portion may not contribute to the electrode reaction.

他方、上記正極バインダーとして増粘効果の高いものを用いたアルカリ電池は、正極バインダーが水酸化カリウムの電解液を吸収し、膨張することによって、正極合剤３中の正極活物質同士および正極活物質と缶との接触が悪くなり、内部抵抗が増大して、重負荷放電性能が低下してしまうという問題があった。   On the other hand, in the alkaline battery using the above-mentioned positive electrode binder having a high thickening effect, the positive electrode binder absorbs the potassium hydroxide electrolyte and expands, so that the positive electrode active materials in the positive electrode mixture 3 and the positive electrode active materials are expanded. There was a problem that the contact between the substance and the can deteriorated, the internal resistance increased, and the heavy load discharge performance deteriorated.

特開２００３−０１７０４２号公報JP 2003-017042 A

本発明は、かかる事情に鑑みてなされたもので、圧入する際に充分なコア強度を有し、かつ使用の際に正極活物質同士および正極活物質と缶との接触不良を防止して、重負荷放電性能に優れる正極合剤を備えたアルカリ電池及びアルカリ電池の製造方法を提供することを目的とする。 The present invention was made in view of such circumstances, has sufficient core strength when press-fitting, and prevents contact between the positive electrode active materials and the positive electrode active material and the can during use, It aims at providing the manufacturing method of an alkaline battery provided with the positive electrode mixture which is excellent in heavy load discharge performance, and an alkaline battery.

上記課題を解決するために、請求項１に記載の発明は、二酸化マンガン及びオキシ水酸化ニッケルの少なくとも何れか一方の正極活物質、正極バインダー並びに水酸化カリウムを含有する正極合剤が圧入された有底筒状の正極缶内に、水酸化カリウム電解液及び負極剤が充填されるとともに、上記正極缶の開口部に負極端子板が設置されてなるアルカリ電池であって、上記正極バインダーは、カルボキシビニルポリマーであり、４０質量％の水酸化カリウム溶液中に当該カルボキシビニルポリマーを２．０質量％含有させた場合の高濃度粘度が１５０００ｍＰａ・ｓ以上であって、かつ４０質量％の水酸化カリウム溶液中に当該カルボキシビニルポリマーを１．０質量％含有させた場合の低濃度粘度が５００ｍＰａ・ｓ以下であるとともに、上記高濃度粘度／上記低濃度粘度の比が５０以上であり、その質量が組立後の電池の正極合剤中の水分質量の１／１００以下であることを特徴としている。 In order to solve the above-mentioned problems, in the invention described in claim 1, a positive electrode mixture containing at least one positive electrode active material of manganese dioxide and nickel oxyhydroxide, a positive electrode binder, and potassium hydroxide is press-fitted. A bottomed cylindrical positive electrode can is filled with a potassium hydroxide electrolyte and a negative electrode agent, and an alkaline battery in which a negative electrode terminal plate is installed in the opening of the positive electrode can, wherein the positive electrode binder comprises: A carboxyvinyl polymer having a high concentration viscosity of 15000 mPa · s or more when 40% by mass of the carboxyvinyl polymer is contained in 40% by mass of potassium hydroxide solution, and 40% by mass of hydroxide The low concentration viscosity when the carboxyvinyl polymer is contained by 1.0% by mass in the potassium solution is 500 mPa · s or less, The high concentration of the viscosity / the low concentration Ri der ratio 50 more viscosity, its mass is characterized by less than 1/100 der Rukoto water mass in the positive electrode mixture of the battery after assembly.

一方、請求項２に記載の発明は、二酸化マンガン及びオキシ水酸化ニッケルの少なくとも何れか一方の正極活物質並びにカルボキシビニルポリマーからなる正極バインダーを混合した後に、水酸化カリウム溶液を加えて湿式混合し、この湿式混合物を顆粒状に粉砕して、所定の形状にプレス成形する正極合剤の形成工程と、この正極合剤を有底筒状の正極缶内に圧入した後に、当該正極缶内に水酸化カリウム電解液及び負極剤を充填して、上記正極缶の開口部に負極端子板を設置する組み立て工程とを有するアルカリ電池の製造方法であって、上記正極バインダーとして、４０質量％の水酸化カリウム溶液中に当該カルボキシビニルポリマーを２．０質量％含有させた場合の高濃度粘度が１５０００ｍＰａ・ｓ以上であって、かつ４０質量％の水酸化カリウム溶液中に当該カルボキシビニルポリマーを１．０質量％含有させた場合の低濃度粘度が５００ｍＰａ・ｓ以下であるものを用いるとともに、上記正極合剤の形成工程によって得られた正極合剤中の上記正極バインダーの質量を、当該正極合剤中の水分質量の１．５％以上とし、かつ上記組み立て工程によって得られたアルカリ電池の上記正極合剤中の上記正極バインダーの質量を、当該正極合剤中の水分質量の１．０％以下としたことを特徴としている。 On the other hand, in the invention according to claim 2, after mixing at least one positive electrode active material of manganese dioxide and nickel oxyhydroxide and a positive electrode binder made of carboxyvinyl polymer, a potassium hydroxide solution is added and wet mixed. The wet mixture is pulverized into granules and press-molded into a predetermined shape, and the positive electrode mixture is press-fitted into a bottomed cylindrical positive can. An alkaline battery manufacturing method comprising an assembly step of filling a potassium hydroxide electrolyte solution and a negative electrode agent and installing a negative electrode terminal plate in the opening of the positive electrode can , wherein 40% by mass of water is used as the positive electrode binder. When the carboxyvinyl polymer is contained in an amount of 2.0% by mass in the potassium oxide solution, the high concentration viscosity is 15000 mPa · s or more and 40% by mass With use of lower concentrations viscosity when the carboxy of carboxyvinyl polymer is contained 1.0 mass% in the potassium hydroxide solution is not more than 500 mPa · s, the positive electrode mixture obtained by the step of forming the positive electrode mixture The mass of the positive electrode binder in the positive electrode mixture is 1.5% or more of the moisture mass in the positive electrode mixture, and the mass of the positive electrode binder in the positive electrode mixture of the alkaline battery obtained by the assembly step is It is characterized by being 1.0% or less of the moisture mass in the positive electrode mixture.

請求項１に記載のアルカリ電池によれば、正極バインダーとして、４０質量％の水酸化カリウム溶液中に当該正極バインダーを２．０質量％含有させた場合の高濃度粘度が１５０００ｍＰａ・ｓ以上であって、かつ４０質量％の水酸化カリウム溶液中に当該正極バインダーを１．０質量％含有させた場合の低濃度粘度が５００ｍＰａ・ｓ以下であるものを用いたため、正極合剤を正極缶内に圧入する際には、正極バインダーの濃度が高く、正極合剤に必要とされるコア強度を付与することができるとともに、使用の際には、セパレータに含浸された電解液等による正極バインダーの濃度低下によって正極バインダーの粘度が低下することにより、水酸化カリウム電解液の浸み込みによる正極合剤の膨張を防止することができる。 According to the alkaline battery of claim 1, as the positive electrode binder, the high concentration viscosity when the positive electrode binder is contained in an amount of 2.0% by mass in a 40% by mass potassium hydroxide solution is 15000 mPa · s or more. In addition, since the low-concentration viscosity when 1.0% by mass of the positive electrode binder is contained in a 40% by mass potassium hydroxide solution is 500 mPa · s or less, the positive electrode mixture is placed in the positive electrode can. When press-fitting, the concentration of the positive electrode binder is high, so that the core strength required for the positive electrode mixture can be imparted, and in use, the concentration of the positive electrode binder by the electrolytic solution impregnated in the separator, etc. By reducing the viscosity of the positive electrode binder due to the decrease, it is possible to prevent the positive electrode mixture from expanding due to the penetration of the potassium hydroxide electrolyte.

その結果、正極合剤を正極缶内に圧入する際には、正極合剤に割れ等の破壊が生じることを防止できるとともに、アルカリ電池の使用の際には、正極活物質同士の接触悪化を防止して、正極缶内の内部抵抗の増大による重負荷放電性能の阻害を防止できる。   As a result, when the positive electrode mixture is pressed into the positive electrode can, the positive electrode mixture can be prevented from being broken or broken, and when using an alkaline battery, the contact deterioration between the positive electrode active materials can be prevented. Therefore, it is possible to prevent the heavy load discharge performance from being hindered due to the increase in internal resistance in the positive electrode can.

特に、４０質量％の水酸化カルシウム中における高濃度粘度／低濃度粘度の比が５０以上となる正極バインダーを用いることによって、時間の経過とともに正極合剤が水酸化カリウム電解液を吸収することによる正極合剤の膨張を防止し、アルカリ電池保存後の正極缶内の内部抵抗の増大を防止することができる。 In particular , by using a positive electrode binder in which the ratio of high concentration viscosity / low concentration viscosity in 40 mass% calcium hydroxide is 50 or more, the positive electrode mixture absorbs the potassium hydroxide electrolyte over time. Can prevent the expansion of the positive electrode mixture and prevent the increase in the internal resistance in the positive electrode can after being stored in an alkaline battery.

また、このような正極バインダーとしては、ポリアクリル酸やポリアクリル酸ナトリウムなどのカルボキシビニルポリマーを好適に用いることができる。加えて、このカルボキシビニルポリマーを、その質量が正極合剤中の正極活物質や水酸化カリウム溶液の溶媒である水等の水分質量の１／１００以下となるように含有させることによって、アルカリ電池保存後の内部抵抗の増大を防止することができる。 Further, as such a positive electrode binder may be a carboxyvinyl polymer, such as polyacrylic acid or sodium polyacrylate suitably. In addition, by adding this carboxyvinyl polymer so that the mass thereof becomes 1/100 or less of the moisture mass of water such as the positive electrode active material in the positive electrode mixture or the solvent of the potassium hydroxide solution, an alkaline battery is obtained. An increase in internal resistance after storage can be prevented.

さらに、請求項２に記載のアルカリ電池の製造方法によれば、正極合剤の形成工程によって得られた正極合剤中のカルボキシビニルポリマーからなる正極バインダーの質量を、当該正極合剤中の水分質量の１．５％以上とすることによって、正極缶内への圧入の際に、正極合剤に必要とされる増粘効果を付与することができる。加えて、組み立て工程によって得られたアルカリ電池の正極合剤中の正極バインダーの質量を、当該正極合剤中の水分質量の１．０％以下とすることによって、アルカリ電池使用の際の正極活物質同士および正極活物質と缶との接触悪化を防止して、内部抵抗の増大による重負荷放電性能の阻害を防止できるとともに、時間の経過による正極合剤の水酸化カリウム電解液の吸収による膨張を防止し、アルカリ電池保存後の正極缶内の内部抵抗の増大を防止することができる。 Furthermore, according to the method for producing an alkaline battery according to claim 2 , the mass of the positive electrode binder composed of the carboxyvinyl polymer in the positive electrode mixture obtained by the step of forming the positive electrode mixture is determined based on the moisture in the positive electrode mixture. By setting the mass to 1.5% or more, the thickening effect required for the positive electrode mixture can be imparted during press-fitting into the positive electrode can. In addition, by setting the mass of the positive electrode binder in the positive electrode mixture of the alkaline battery obtained by the assembly process to 1.0% or less of the moisture mass in the positive electrode mixture, the positive electrode active when using the alkaline battery is reduced. Prevents deterioration of contact between materials and cathode active material and can, prevents heavy load discharge performance from being hindered by increase in internal resistance, and expands due to absorption of potassium hydroxide electrolyte in cathode mixture over time It is possible to prevent the increase in internal resistance in the positive electrode can after being stored in an alkaline battery.

本発明に係るアルカリ電池の一実施形態について説明する。
本実施形態のアルカリ電池は、上記正極合剤３が二酸化マンガンからなる正極活物質、黒鉛、正極バインダー並びに４０質量％の水酸化カリウム水溶液を含有している。そして、この正極合剤３は、軸線方向を正極缶１の軸線方向に向けて圧入されるとともに、正極缶１の軸線方向に沿って複数本（本実施形態においては３本）装填されている。 An embodiment of an alkaline battery according to the present invention will be described.
In the alkaline battery of the present embodiment, the positive electrode mixture 3 contains a positive electrode active material made of manganese dioxide, graphite, a positive electrode binder, and a 40% by mass potassium hydroxide aqueous solution. The positive electrode mixture 3 is pressed into the axial direction of the positive electrode can 1 along the axial direction, and a plurality (three in the present embodiment) are loaded along the axial direction of the positive electrode can 1. .

この正極バインダーとしては、４０質量％の水酸化カリウム水溶液中に当該正極バインダーを２．０質量％含有させた場合の高濃度粘度が１５０００ｍＰａ・ｓ以上であって、かつ４０質量％の水酸化カリウム水溶液中に当該正極バインダーを１．０質量％含有させた場合の低濃度粘度が５００ｍＰａ・ｓ以下であるものが用いられ、好ましくは上記高濃度粘度／上記低濃度粘度の比が５０以上であるものが用いられる。このような正極バインダーとしては、ポリアクリル酸やポリアクリル酸ナトリウム等のカルボキシビニルポリマーが用いられる。 The positive electrode binder has a high concentration viscosity of 15000 mPa · s or higher when 40% by mass of the positive electrode binder is contained in 40% by mass of potassium hydroxide aqueous solution, and 40% by mass of potassium hydroxide. those low concentrations viscosity when the positive electrode binder were contained 1.0% by weight in the aqueous solution is not more than 5 00 mPa · s is used, preferably the ratio of the high density / viscosity above low concentrations viscosity more than 50 Is used. As such a positive electrode binder, a carboxyvinyl polymer such as polyacrylic acid or sodium polyacrylate is used.

さらに、アルカリ電池は、正極合剤３内に有底円筒状のセパレータ４が収容されるとともに、このセパレータ４は、正極合剤３とともに水酸化カリウム水溶液が含浸されている。そして、このセパレータ４内に亜鉛粉が強アルカリ液に混合されてなるゲル状の負極剤５が所定の高さまで注入されるとともに、この負極剤５内に真鍮製の集電棒６が所定の深さまで挿入されている。   Further, in the alkaline battery, a bottomed cylindrical separator 4 is accommodated in the positive electrode mixture 3, and the separator 4 is impregnated with an aqueous potassium hydroxide solution together with the positive electrode mixture 3. A gel-like negative electrode agent 5 in which zinc powder is mixed with a strong alkaline solution is injected into the separator 4 to a predetermined height, and a brass current collector 6 is inserted into the negative electrode agent 5 at a predetermined depth. It has been inserted.

さらに、正極缶１の上端開口部には、絶縁性のガスケット１０を介して当該開口部を塞ぐ略円板状の負極端子板１１が設けられている。このガスケット１０の中央部には、中心に集電棒６を挿入する孔部１０ａが形成されるとともに、当該集電棒６を所定の長さ寸法囲繞する厚肉円筒状の封止部１０ｂが一体に形成されている。そして、この封止部１０ｂが集電棒６の外周面に密着することにより、正極缶１内の電解液が集電棒６の外周面を伝って負極側から漏れることが防止されるとともに、この集電棒６の頭頂部６ａが負極端子板１１に溶接接続されている。   Furthermore, a substantially disc-shaped negative electrode terminal plate 11 is provided at the upper end opening of the positive electrode can 1 via an insulating gasket 10 to close the opening. A hole 10a for inserting the current collecting rod 6 is formed at the center of the gasket 10, and a thick cylindrical sealing portion 10b surrounding the current collecting rod 6 with a predetermined length is integrally formed. Is formed. And since this sealing part 10b closely_contact | adheres to the outer peripheral surface of the current collector rod 6, it is prevented that the electrolyte solution in the positive electrode can 1 leaks from the negative electrode side along the outer peripheral surface of the current collector rod 6, and this current collector. The top 6 a of the electric rod 6 is connected to the negative terminal plate 11 by welding.

上述のようにして組み立てられたアルカリ電池は、このガスケット１０によって正極缶１と負極端子板１１との絶縁性が確保されており、上記正極バインダーとしてのカルボキシビニルポリマーの質量がマンガンの結晶水や水酸化カリウム水溶液中における水等の水分質量の１．０％以下となるように調製されている。   In the alkaline battery assembled as described above, insulation between the positive electrode can 1 and the negative electrode terminal plate 11 is ensured by the gasket 10, and the mass of the carboxyvinyl polymer as the positive electrode binder is manganese crystallization water or It is prepared so that it may become 1.0% or less of moisture mass, such as water in potassium hydroxide aqueous solution.

次いで、本発明に係る上記アルカリ電池の製造方法について説明する。
本実施形態のアルカリ電池の製造方法は、上述の円筒状の正極合剤を形成する正極合剤の形成工程と、この正極合剤を正極缶内に圧入し、アルカリ電池を製造する組み立て工程とを有する。 Next, a method for producing the alkaline battery according to the present invention will be described.
The alkaline battery manufacturing method of the present embodiment includes a positive electrode mixture forming process for forming the above-described cylindrical positive electrode mixture, and an assembly process for manufacturing the alkaline battery by press-fitting the positive electrode mixture into the positive electrode can. Have

まず、上記正極合剤の形成工程においては、正極活物質としての二酸化マンガン粉体に、黒鉛粉体、正極バインダーとしてのカルボキシビニルポリマー及び４０質量％の水酸化カリウム水溶液を加えて湿式混合し、この湿式混合粉体（湿式混合物）をローラコンパクタにて圧延し、シート状にする。次いで、このシート状の湿式混合粉体を顆粒状に粉砕した後に、この顆粒状物を円筒状のキャビティが形成された金型に入れて、プレス成形することによって、円筒状の正極合剤３を形成する。   First, in the step of forming the positive electrode mixture, graphite powder, a carboxyvinyl polymer as a positive electrode binder, and a 40% by mass potassium hydroxide aqueous solution are added to manganese dioxide powder as a positive electrode active material and wet mixed. This wet mixed powder (wet mixture) is rolled with a roller compactor to form a sheet. Next, after this sheet-like wet mixed powder is pulverized into granules, the granules are placed in a mold having a cylindrical cavity and press-molded, whereby a cylindrical positive electrode mixture 3 is obtained. Form.

その際、カルボキシビニルポリマーの質量を、二酸化マンガンの結晶水や水酸化カリウム水溶液中に含有される６０質量％の水等の水分質量の１．５％以上となるように調製している。   At this time, the mass of the carboxyvinyl polymer is adjusted to be 1.5% or more of the water mass such as 60% by mass of water contained in the crystal water of manganese dioxide or the aqueous potassium hydroxide solution.

次いで、上記組み立て工程においては、複数本（本実施形態においては３本）の正極合剤３を、当該正極合剤３の軸線方向を有底円筒状の正極缶１の軸線方向に向けて、当該正極合剤３の外周面が正極缶１の内周壁面に形成された導電膜２に接するように圧入する。   Next, in the assembly process, a plurality (three in the present embodiment) of the positive electrode mixture 3 is directed so that the axial direction of the positive electrode mixture 3 is directed to the axial direction of the bottomed cylindrical positive electrode can 1. The positive electrode mixture 3 is press-fitted so that the outer peripheral surface of the positive electrode mixture 3 is in contact with the conductive film 2 formed on the inner peripheral wall surface of the positive electrode can 1.

次いで、正極合剤３内に有底円筒状のセパレータ４を収容した後に、正極缶１内に４０質量％の水酸化カリウム電解液を注入し、その後、正極合剤３中に亜鉛粉が強アルカリ液に混合されてなるゲル状の負極剤５を所定の高さまで注入する。そして、この負極剤５内に真鍮製の集電棒６を挿入し、正極缶１の上端開口部にガスケット１０及び集電棒６の頭頂部６ａに溶接された負極端子板１１等を配設することによって、アルカリ電池を組み立てた。   Next, after the bottomed cylindrical separator 4 is accommodated in the positive electrode mixture 3, a 40 mass% potassium hydroxide electrolyte is injected into the positive electrode can 1, and then the zinc powder is strong in the positive electrode mixture 3. A gelled negative electrode agent 5 mixed with an alkaline solution is poured to a predetermined height. Then, a brass current collector rod 6 is inserted into the negative electrode agent 5, and a gasket 10 and a negative electrode terminal plate 11 welded to the top 6 a of the current collector rod 6 are disposed in the upper end opening of the positive electrode can 1. An alkaline battery was assembled.

これによって得られたアルカリ電池は、カルボキシビニルポリマーの質量が正極缶１内の水酸化カリウム電解液等の充填により、水分質量の１．０％以下となるように調製されており、時間経過による内部抵抗の増大が抑制される。   The alkaline battery thus obtained is prepared such that the mass of the carboxyvinyl polymer is 1.0% or less of the moisture mass by filling with the potassium hydroxide electrolyte solution or the like in the positive electrode can 1. Increase in internal resistance is suppressed.

次いで、正極バインダーの粘度変化等による正極合剤のコア強度やアルカリ電池の内部抵抗の変化等について、各種実験を行った。   Next, various experiments were conducted on changes in the core strength of the positive electrode mixture and the internal resistance of the alkaline battery due to changes in the viscosity of the positive electrode binder.

［実験例１］高濃度粘度とコア強度との関係
まず、試料Ｎｏ．１−１〜１−３としてポリアクリル酸を用意するとともに、試料Ｎｏ．１−４としてポリエチレンを、同試料１−５〜１−７としてポリアクリル酸をそれぞれ用意した。 [Experimental Example 1] Relationship between High Concentration Viscosity and Core Strength While preparing polyacrylic acid as 1-1 to 1-3, sample no. Polyethylene was prepared as 1-4, and polyacrylic acid was prepared as samples 1-5 to 1-7.

次いで、各試料１−１〜１−７の正極バインダーを、それぞれ４０質量％の水酸化カリウム水溶液中に２．０質量％となるように添加した試料の粘度（高濃度粘度）を、ブルックフィールド（商標名）回転粘度計ＤＶ−１＋（ブルックフィールド製）によって、スピンドルＮｏ．ＬＶ―５を用いて計測し、表１に示した。   Next, the viscosity (high concentration viscosity) of the sample obtained by adding the positive electrode binder of each of the samples 1-1 to 1-7 to 2.0% by mass in a 40% by mass potassium hydroxide aqueous solution was determined by Brookfield. (Trade name) Rotational viscometer DV-1 + (manufactured by Brookfield) Measured using LV-5 and shown in Table 1.

次いで、上述の各試料１０質量部に、それぞれ９０質量部のＥＭＤ粉体及び７質量部のグラファイト粉体を混合するとともに、これらの粉体混合物にそれぞれ３質量部の４０質量％の水酸化カリウム水溶液を加えて、湿式混合した。   Next, 90 parts by mass of EMD powder and 7 parts by mass of graphite powder were mixed with 10 parts by mass of each of the above-mentioned samples, and 3 parts by mass of 40% by mass of potassium hydroxide were added to these powder mixtures. The aqueous solution was added and wet mixed.

次ぎに、この湿式混合粉体をローラコンパクタによって圧延し、シート状にした後に、このシート状の湿式混合粉体を顆粒状に粉砕し、この顆粒状粉体を円筒状のキャビティが形成された金型に入れてプレス成形することによって、正極合剤を作成した。これにより、得られた円筒状の正極合剤のコア寸法は、外形が１３．４ｍｍ、内径が９．０ｍｍ、軸線方向高さが１３．５ｍｍ、重量が３．４５ｇ、成形密度が３．３０ｇ／ｃｍ3であった。 Next, the wet mixed powder was rolled with a roller compactor to form a sheet, and then the wet mixed powder in the form of a sheet was pulverized into a granular form, and a cylindrical cavity was formed in the granular powder. A positive electrode mixture was prepared by press molding in a mold. As a result, the core dimensions of the obtained cylindrical positive electrode mixture are as follows: the outer shape is 13.4 mm, the inner diameter is 9.0 mm, the axial height is 13.5 mm, the weight is 3.45 g, and the molding density is 3.30 g. / Cm 3 .

次いで、各正極合剤を、軸線方向を水平方向に向けて水平試験台上に載置し、各正極合剤の上方から下方に向けて漸次高圧の圧力を加え、割れた際の圧力をコア強度として計測し、それぞれ表１に示すとともに、各正極合剤の正極バインダーの高濃度粘度に対するコア強度を図１に線グラフにして示した。   Next, each positive electrode mixture is placed on a horizontal test stand with the axial direction being horizontal, and a gradually increasing pressure is applied from the top to the bottom of each positive electrode mixture. The strength was measured and shown in Table 1, and the core strength with respect to the high concentration viscosity of the positive electrode binder of each positive electrode mixture was shown as a line graph in FIG.

Figure 0005622996
Figure 0005622996

表１及び図１から判るように、正極バインダーとして、４０質量％の水酸化カリウム水溶液中に当該正極バインダーを２質量％含有させた場合の高濃度粘度が１５０００ｍｐａ・ｓ以上であるものを用いて、正極合剤を作成すると、著しくコア強度が増大する。故に、この正極合剤を正極缶内に圧入する際には、正極合剤の割れ等の破壊を効率的に防止することができる。   As can be seen from Table 1 and FIG. 1, a positive electrode binder having a high concentration viscosity of 15000 mpa · s or more when 2% by mass of the positive electrode binder is contained in a 40% by mass potassium hydroxide aqueous solution is used. When the positive electrode mixture is prepared, the core strength is remarkably increased. Therefore, when this positive electrode mixture is pressed into the positive electrode can, breakage such as cracking of the positive electrode mixture can be efficiently prevented.

［実験例２］低濃度粘度と初度内部抵抗値との関係
試料Ｎｏ．２−１〜２−６として、ポリアクリル酸を用意して、スピンドルＮｏ．ＬＶ―５をＬＶ−２に代えたことを除き、実験例１と同様に、各試料の粘度を計測し、表２に示した。 [Experimental Example 2] Relationship between low concentration viscosity and initial internal resistance value As 2-1 to 2-6, polyacrylic acid was prepared. The viscosity of each sample was measured and shown in Table 2 in the same manner as in Experimental Example 1 except that LV-5 was replaced with LV-2.

次いで、各試料Ｎｏ．２−１〜２−６を用いて、それぞれ実験例１と同様に
３本の正極合剤を作成し、各同一試料から作成された３本の正極合剤をそれぞれ同一の正極缶内に圧入して、これらの正極合剤内にセパレータを収容した後に、４０質量％の水酸化カリウム電解液を注入した。次いで、６５質量％の亜鉛粉が強アルカリ液（４０質量％ＫＯＨ／３．０％ＺｎＯ）に混合されてなるゲル状の負極剤５を充填し、集電棒６を挿入して、アルカリ電池を組み立てた。 Then, each sample No. Using 2-1 to 2-6, three positive electrode mixtures were prepared in the same manner as in Experimental Example 1, and the three positive electrode mixtures prepared from the same samples were respectively pressed into the same positive electrode cans. And after accommodating a separator in these positive electrode mixtures, 40 mass% potassium hydroxide electrolyte solution was inject | poured. Next, the gelled negative electrode agent 5 in which 65% by mass of zinc powder is mixed with a strong alkaline solution (40% by mass KOH / 3.0% ZnO) is filled, and the current collector rod 6 is inserted, whereby an alkaline battery is obtained. Assembled.

これにより得られた各単３形のアルカリ電池（ＬＲ６）の初度の内部抵抗値を計測し、表２に示すとともに、各アルカリ電池の正極バインダーの低濃度粘度に対するアルカリ電池の初度内部抵抗値を図２に線グラフにして示した。   The initial internal resistance value of each AA alkaline battery (LR6) thus obtained was measured and shown in Table 2, and the initial internal resistance value of the alkaline battery with respect to the low concentration viscosity of the positive electrode binder of each alkaline battery was determined. A line graph is shown in FIG.

Figure 0005622996
Figure 0005622996

表２及び図２から判るように、正極バインダーとして、４０質量％の水酸化カリウム水溶液中に正極バインダーを１質量％含有させた場合の低濃度粘度が５００ｍｐａ・ｓ以下であるものを用いたアルカリ電池は、初度内部抵抗値が９０以下である。これに対して、正極バインダーの低濃度粘度が５００ｍｐａ・ｓを超えたアルカリ電池は、著しく初度内部抵抗値が増加してしまう。故に、低濃度粘度が５００ｍｐａ・ｓ以下である正極バインダーを用いてアルカリ電池を製造することによって、正極缶内の内部抵抗の増大による重負荷放電性能の阻害を防止できる。 As can be seen from Table 2 and FIG. 2, use as a positive electrode binder, those low concentrations viscosity when the positive electrode binder was contained 1% by weight in a 40 wt% aqueous solution of potassium hydroxide is less than 5 00 mpa · s The alkaline battery had an initial internal resistance value of 90 or less. In contrast, the alkaline battery low concentrations viscosity of the positive electrode binder exceeds 5 00 mpa · s, the increases considerably first-time internal resistance. Therefore, by producing an alkaline battery using a positive electrode binder low concentrations the viscosity is less than 5 00 mpa · s, can be prevented inhibition of heavy load discharge performance due to increased internal resistance of the positive electrode can.

［実験例３］粘度比とアルカリ電池保存後の内部抵抗との関係
高濃度粘度が２００００ｍｐａ・ｓである試料Ｎｏ．３−１、３−２及び３−１１、３−１３として、ポリアクリル酸を用意して、各試料の低濃度粘度を実験例２と同様に計測して表３に示した。また、低濃度粘度が４５０ｍｐａ・ｓである試料３−４、３−５及び３−１２、３−１３として、ポリアクリル酸を用意して、各試料の高濃度粘度を実験例１と同様に計測して表３に示した。さらに、各試料の高濃度粘度／低濃度粘度の比を計算して表３に示した。 [Experimental Example 3] Relationship between viscosity ratio and internal resistance after storage in alkaline battery Sample No. 2 having a high concentration viscosity of 20000 mpa · s. 3-1, 3-2 and 3-11, as 3-13, are prepared polyacrylic acid, shown in Table 3 was measured similarly low concentrations viscosity of each sample as in Experimental Example 2. Further, as samples 3-4, 3-5, 3-12 , and 3-13 having a low concentration viscosity of 450 mpa · s, polyacrylic acid was prepared, and the high concentration viscosity of each sample was the same as in Experimental Example 1. The measured values are shown in Table 3. Further, the ratio of high concentration viscosity / low concentration viscosity of each sample was calculated and shown in Table 3.

その後、各試料によって実験例１と同様に作成した正極合剤を用いて、実験例２と同様にアルカリ電池を製造し、６０度で２０日間保存した後の内部抵抗（交流法１ｋＨｚ）を計測し、表３に示した。そして、高濃度粘度が２００００ｍｐａ・ｓである正極バインダーを用いた場合の高濃度粘度／低濃度粘度の比に対するアルカリ電池の内部抵抗と、低濃度粘度が４５０ｍｐａ・ｓである正極バインダーを用いた場合の高濃度粘度／低濃度粘度の比に対するアルカリ電池の内部抵抗とを図３に線グラフにして示した。 Then, using the positive electrode mixture prepared in the same manner as in Experimental Example 1 with each sample, an alkaline battery was manufactured in the same manner as in Experimental Example 2, and the internal resistance (AC method 1 kHz) after storage at 60 degrees for 20 days was measured. The results are shown in Table 3. Then, use the internal resistance of the alkaline battery with respect to the ratio of high density / viscosity low concentrations viscosity in the case of using the positive electrode binder high concentration viscosity of 2000 0 mpa · s, the positive electrode binder low concentrations viscosity of 450 MPa · s FIG. 3 is a line graph showing the internal resistance of the alkaline battery with respect to the ratio of high concentration viscosity / low concentration viscosity.

Figure 0005622996
Figure 0005622996

表３及び図３からわかるように、高濃度粘度が２００００ｍｐａ・ｓである正極バインダーを用いても、低濃度粘度が４５０ｍｐａ・ｓである正極バインダーを用いても、高濃度粘度／低濃度粘度の比が５０以上であると、上記保存後の内部抵抗が著しく低下し、時間の経過による正極缶内の内部抵抗の増大を防止できる。 As can be seen from Table 3 and FIG. 3, even when using a positive electrode binder having a high concentration viscosity of 2000 0 mpa · s or using a positive electrode binder having a low concentration viscosity of 450 mpa · s, high concentration viscosity / low concentration When the viscosity ratio is 50 or more, the internal resistance after the storage is remarkably lowered, and an increase in the internal resistance in the positive electrode can with time can be prevented.

［実験例４］正極合剤の正極バインダー質量／水分質量の比とコア強度との関係
試料Ｎｏ．４−１〜４−６として、ポリアクリル酸を用意し、実験例１と同様に、各試料を用いて正極合剤を作成した。その際、各種粉体や水酸化カリウム水溶液等の割合を、各試料の正極バインダー質量／水分質量の比を表４に示す割合にすべく調製した。
次いで、これらの各試料のコア強度を、実験例１と同様の方法で計測し、表４に示すとともに、上記正極バインダー質量／水分質量の比に対するコア強度を図４に線グラフにして示した。 [Experimental Example 4] Relationship between the ratio of the positive electrode binder mass / moisture mass of the positive electrode mixture and the core strength As 4-1 to 4-6, polyacrylic acid was prepared, and a positive electrode mixture was prepared using each sample in the same manner as in Experimental Example 1. At that time, the ratios of various powders and aqueous potassium hydroxide solution were prepared so that the ratio of the positive electrode binder mass / water mass of each sample was the ratio shown in Table 4.
Next, the core strength of each of these samples was measured by the same method as in Experimental Example 1 and shown in Table 4, and the core strength with respect to the positive electrode binder mass / water mass ratio was shown as a line graph in FIG. .

Figure 0005622996
Figure 0005622996

表４及び図４から判るように、正極バインダー質量／水分質量が１．５％以上であると、コア強度が６．５Ｎ以上で安定しているのに対して、１．５％未満であると、著しくコア強度が低下している。故に、正極バインダーの質量／水分質量を１．５％以上にすることによって、正極缶内に圧入する際の正極合剤の割れ等を効率的に防止することができる。   As can be seen from Table 4 and FIG. 4, when the positive electrode binder mass / water mass is 1.5% or more, the core strength is stable at 6.5 N or more, whereas it is less than 1.5%. The core strength is significantly reduced. Therefore, by setting the mass / moisture content of the positive electrode binder to 1.5% or more, it is possible to efficiently prevent cracking of the positive electrode mixture when it is press-fitted into the positive electrode can.

［実験例５］アルカリ電池の正極バインダー質量／水分質量の比とアルカリ電池保存後の内部抵抗との関係
試料Ｎｏ．５−１〜５−６として、ポリアクリル酸を用意し、各試料を用いて、実験例２と同様に単３形のアルカリ電池を作成した。その際、各種粉体や水酸化カリウム水溶液等の割合を、アルカリ電池の正極バインダー質量／水分質量の比が表５に示すように０．５〜２．０の範囲となるように調製した。 [Experimental Example 5] Relationship between the ratio of the positive electrode binder mass / water mass of the alkaline battery and the internal resistance after storage of the alkaline battery Polyacrylic acid was prepared as 5-1 to 5-6, and AA alkaline batteries were prepared using each sample in the same manner as in Experimental Example 2. At that time, the proportions of various powders, potassium hydroxide aqueous solution, and the like were prepared such that the ratio of the positive electrode binder mass / water mass of the alkaline battery was in the range of 0.5 to 2.0 as shown in Table 5.

次いで、これら各試料の内部抵抗を、実験例３と同様の方法で計測し、表５に示すとともに、上記正極バインダー質量／水分質量の比に対する内部抵抗を図５に線グラフにして示した。   Next, the internal resistance of each of these samples was measured by the same method as in Experimental Example 3 and shown in Table 5, and the internal resistance with respect to the positive electrode binder mass / water mass ratio was shown as a line graph in FIG.

Figure 0005622996
Figure 0005622996

表５及び図５から判るように、アルカリ電池は、正極バインダー質量／水分質量の比が１．０％以下であると、６０度で２０日間保存後の内部抵抗が１１０ｍΩ以下で安定しているのに対して、上記質量比が１．０％を超えると、上記保存後の内部抵抗が著しく増加している。   As can be seen from Table 5 and FIG. 5, when the ratio of the positive electrode binder mass / water mass is 1.0% or less, the alkaline battery has a stable internal resistance of 110 mΩ or less after storage at 60 degrees for 20 days. On the other hand, when the mass ratio exceeds 1.0%, the internal resistance after the storage is remarkably increased.

本実施形態のアルカリ電池によれば、高濃度粘度が１５０００ｍＰａ・ｓ以上であって、かつ低濃度粘度が５００ｍＰａ・ｓ以下である正極バインダーを用いたため、正極缶内に圧入する際の正極合剤の割れ等の破壊を効率的に防止することができるとともに、アルカリ電池の組み立ての際の正極合剤への水酸化カリウム電解液の浸み込みを防止することによって、正極合剤の膨張による正極活物質同士および正極活物質と缶との接触悪化を防止できる。その結果、正極合剤の搬送や圧入等の取扱性を良好なものとすることができるとともに、正極缶内の内部抵抗の増大による重負荷放電性能の阻害を防止できる。   According to the alkaline battery of the present embodiment, since the positive electrode binder having a high concentration viscosity of 15000 mPa · s or more and a low concentration viscosity of 500 mPa · s or less is used, the positive electrode mixture at the time of press-fitting into the positive electrode can The positive electrode due to expansion of the positive electrode mixture can be efficiently prevented by preventing the potassium hydroxide electrolyte from penetrating into the positive electrode mixture when assembling the alkaline battery. It is possible to prevent contact deterioration between the active materials and between the positive electrode active material and the can. As a result, it is possible to improve the handling properties such as the conveyance and press-fitting of the positive electrode mixture, and it is possible to prevent the heavy load discharge performance from being hindered due to the increase in the internal resistance in the positive electrode can.

特に、正極バインダーとして、高濃度粘度／低濃度粘度の比が５０以上となるものを用いることによって、時間の経過による正極合剤の水酸化カリウム電解液の吸収による膨張を防止し、アルカリ電池保存後の正極缶内の内部抵抗の増大を防止できる。加えて、正極バインダーとして、カルボキシビニルポリマーを用いるとともに、このカルボキシビニルポリマーの質量を、正極合剤中の正極活物質の結晶水や水酸化カリウム水溶液等による水分質量の１／１００以下に調製したため、アルカリ電池保存後の内部抵抗の増大を一段と効果的に防止することができる。   In particular, by using a positive electrode binder having a high concentration viscosity / low concentration viscosity ratio of 50 or more, it is possible to prevent expansion due to absorption of the potassium hydroxide electrolyte of the positive electrode mixture over time, and storage in an alkaline battery. The increase in internal resistance in the positive electrode can later can be prevented. In addition, since a carboxyvinyl polymer was used as the positive electrode binder, the mass of the carboxyvinyl polymer was adjusted to 1/100 or less of the water mass due to crystallization water or potassium hydroxide aqueous solution of the positive electrode active material in the positive electrode mixture. Further, it is possible to effectively prevent the increase in internal resistance after storage of the alkaline battery.

さらに、本実施形態のアルカリ電池の製造方法によれば、正極合剤の形成工程によって得られた正極合剤中のカルボキシビニルポリマーからなる正極バインダーの質量を、当該正極合剤中の水分質量の１．５％以上とするとともに、組み立て工程によって得られたアルカリ電池の正極合剤中の正極バインダーの質量を、当該正極合剤中の水分質量の１．０％以下とすることによって、正極缶内への圧入の際に必要とされる増粘効果を正極合剤に付与することができるとともに、使用の際や保管後における内部抵抗の増大を防止することができる。その結果、正極合剤の搬送や圧入等の取扱性を良好なものとすることができるとともに、正極缶内の内部抵抗の増大による重負荷放電性能の阻害を防止できる。   Furthermore, according to the method for producing an alkaline battery of the present embodiment, the mass of the positive electrode binder composed of the carboxyvinyl polymer in the positive electrode mixture obtained by the step of forming the positive electrode mixture is set to the moisture mass in the positive electrode mixture. By making the mass of the positive electrode binder in the positive electrode mixture of the alkaline battery obtained by the assembly process to be 1.5% or more and 1.0% or less of the moisture mass in the positive electrode mixture, the positive electrode can A thickening effect required in press-fitting into the inside can be imparted to the positive electrode mixture, and an increase in internal resistance during use and after storage can be prevented. As a result, it is possible to improve the handling properties such as the conveyance and press-fitting of the positive electrode mixture, and it is possible to prevent the heavy load discharge performance from being hindered due to the increase in the internal resistance in the positive electrode can.

なお、本発明は、上述の実施形態に何ら限定されるものでなく、例えば、正極活物質としてオキシ水酸化ニッケルを用いてもよい。   In addition, this invention is not limited to the above-mentioned embodiment at all, For example, you may use nickel oxyhydroxide as a positive electrode active material.

各正極合剤の正極バインダー高濃度粘度（ｍｐａ・ｓ）に対するコア強度（Ｎ）を示した線グラフである。It is the line graph which showed the core intensity | strength (N) with respect to the positive electrode binder high concentration viscosity (mpa * s) of each positive electrode mixture. 各アルカリ電池の正極バインダーの低濃度粘度（ｍｐａ・ｓ）に対するアルカリ電池の初度内部抵抗値（ｍΩ）を示した線グラフである。It is the line graph which showed the initial stage internal resistance value (m (ohm)) of the alkaline battery with respect to the low concentration viscosity (mpa * s) of the positive electrode binder of each alkaline battery. 高濃度粘度が２００００ｍｐａ・ｓである正極バインダーを用いた場合の高濃度粘度／低濃度粘度の比に対するアルカリ電池の保存後の内部抵抗（ｍΩ）と、低濃度粘度が４５０ｍｐａ・ｓである正極バインダーを用いた場合の高濃度粘度／低濃度粘度の比に対するアルカリ電池の保存後の内部抵抗（ｍΩ）とを示した線グラフである。Internal resistance (mΩ) after storage of an alkaline battery with respect to the ratio of high concentration viscosity / low concentration viscosity when using a positive electrode binder having a high concentration viscosity of 20000 mpa · s, and a positive electrode binder having a low concentration viscosity of 450 mpa · s 6 is a line graph showing the internal resistance (mΩ) after storage of the alkaline battery with respect to the ratio of the high concentration viscosity / low concentration viscosity when using. 正極合剤の正極バインダー質量／水分質量×１００（％）に対するコア強度（Ｎ）を示した線グラフである。It is the line graph which showed the core intensity | strength (N) with respect to the positive electrode binder mass / moisture mass x100 (%) of a positive mix. アルカリ電池の正極バインダー質量／水分質量×１００（％）に対する保存後の内部抵抗（ｍΩ）を示した線グラフである。It is the line graph which showed the internal resistance (mohm) after the preservation | save with respect to the positive electrode binder mass / moisture mass x100 (%) of an alkaline battery. 本発明に係るアルカリ電池の一実施形態を示す要部の縦断面図である。It is a longitudinal cross-sectional view of the principal part which shows one Embodiment of the alkaline battery which concerns on this invention.

符号の説明Explanation of symbols

１ 正極缶
２ 導電膜
３ 正極合剤
４ セパレータ
５ 負極剤
６ 集電棒
１１負極端子板 DESCRIPTION OF SYMBOLS 1 Positive electrode can 2 Conductive film 3 Positive electrode mixture 4 Separator 5 Negative electrode agent 6 Current collecting rod 11 Negative electrode terminal board

Claims (2)

有底筒状の正極缶内に、二酸化マンガン及びオキシ水酸化ニッケルの少なくとも何れか一方の正極活物質、正極バインダー並びに水酸化カリウムを含有する正極合剤が圧入されるとともに、水酸化カリウム電解液が含浸されたセパレータ及び負極剤が収容され、かつ上記正極缶の開口部に負極端子板が設置されてなるアルカリ電池であって、
上記正極バインダーは、カルボキシビニルポリマーであり、４０質量％の水酸化カリウム溶液中に当該カルボキシビニルポリマーを２．０質量％含有させた場合の高濃度粘度が１５０００ｍＰａ・ｓ以上であって、かつ４０質量％の水酸化カリウム溶液中に当該カルボキシビニルポリマーを１．０質量％含有させた場合の低濃度粘度が５００ｍＰａ・ｓ以下であるとともに、上記高濃度粘度／上記低濃度粘度の比が５０以上であり、その質量が組立後の電池の正極合剤中の水分質量の１／１００以下であることを特徴とするアルカリ電池。 A positive electrode mixture containing at least one of a positive electrode active material of manganese dioxide and nickel oxyhydroxide, a positive electrode binder, and potassium hydroxide is pressed into a bottomed cylindrical positive electrode can, and a potassium hydroxide electrolyte solution Is an alkaline battery in which a separator and a negative electrode agent impregnated are accommodated, and a negative electrode terminal plate is installed in the opening of the positive electrode can,
The positive electrode binder is a carboxyvinyl polymer, and has a high concentration viscosity of 15000 mPa · s or more when 2.0% by mass of the carboxyvinyl polymer is contained in a 40% by mass potassium hydroxide solution, The low concentration viscosity is 500 mPa · s or less when 1.0 mass% of the carboxyvinyl polymer is contained in a mass% potassium hydroxide solution, and the ratio of the high concentration viscosity / the low concentration viscosity is 50 or more. The alkaline battery is characterized in that its mass is 1/100 or less of the moisture mass in the positive electrode mixture of the assembled battery. 二酸化マンガン及びオキシ水酸化ニッケルの少なくとも何れか一方の正極活物質並びにカルボキシビニルポリマーからなる正極バインダーを混合した後に、水酸化カリウム溶液を加えて湿式混合し、この湿式混合物を顆粒状に粉砕して、所定の形状にプレス成形する正極合剤の形成工程と、この正極合剤を有底筒状の正極缶内に圧入した後に、当該正極缶内に水酸化カリウム電解液及び負極剤を充填して、上記正極缶の開口部に負極端子板を設置する組み立て工程とを有するアルカリ電池の製造方法であって、
上記正極バインダーとして、４０質量％の水酸化カリウム溶液中に当該カルボキシビニルポリマーを２．０質量％含有させた場合の高濃度粘度が１５０００ｍＰａ・ｓ以上であって、かつ４０質量％の水酸化カリウム溶液中に当該カルボキシビニルポリマーを１．０質量％含有させた場合の低濃度粘度が５００ｍＰａ・ｓ以下であるものを用いるとともに、上記正極合剤の形成工程によって得られた正極合剤中の上記正極バインダーの質量を、当該正極合剤中の水分質量の１．５％以上とし、かつ上記組み立て工程によって得られたアルカリ電池の上記正極合剤中の上記正極バインダーの質量を、当該正極合剤中の水分質量の１．０％以下としたことを特徴とするアルカリ電池の製造方法。 After mixing the positive electrode active material of at least one of manganese dioxide and nickel oxyhydroxide and the positive electrode binder made of carboxyvinyl polymer, potassium hydroxide solution is added and wet mixed, and this wet mixture is pulverized into granules. After forming the positive electrode mixture into a predetermined shape and press-fitting the positive electrode mixture into the bottomed cylindrical positive electrode can, the positive electrode can is filled with a potassium hydroxide electrolyte and a negative electrode agent. And an assembly process of installing a negative electrode terminal plate in the opening of the positive electrode can,
As the positive electrode binder, a high concentration viscosity is 15000 mPa · s or more when 40% by mass of the carboxyvinyl polymer is contained in 40% by mass of potassium hydroxide solution, and 40% by mass of potassium hydroxide. While using the carboxyvinyl polymer in the solution having a low concentration viscosity of 500 mPa · s or less when 1.0% by mass is contained, the above-mentioned positive electrode mixture obtained by the positive electrode mixture forming step is used. The mass of the positive electrode binder is set to 1.5% or more of the moisture mass in the positive electrode mixture, and the mass of the positive electrode binder in the positive electrode mixture of the alkaline battery obtained by the assembly process is determined as the positive electrode mixture. A method for producing an alkaline battery, characterized in that the moisture content is 1.0% or less.
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