JPS62122060A - Manganese dry battery - Google Patents
Manganese dry batteryInfo
- Publication number
- JPS62122060A JPS62122060A JP60261349A JP26134985A JPS62122060A JP S62122060 A JPS62122060 A JP S62122060A JP 60261349 A JP60261349 A JP 60261349A JP 26134985 A JP26134985 A JP 26134985A JP S62122060 A JPS62122060 A JP S62122060A
- Authority
- JP
- Japan
- Prior art keywords
- manganese dioxide
- carbon black
- electrolyte
- dry battery
- tap density
- 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
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
- H01M4/36—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
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は、マンガン乾電池の高温貯蔵特性の向上に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to improving the high temperature storage characteristics of manganese dry batteries.
「従来の技術」
従来のマンガン乾１！池は、正極作用物質１二二酸化マ
ンガン、負極作用物質（ユ亜鉛、導電補助付兼電解液保
持材にアセチレンブラックを用い、電解液に塩化亜鉛と
塩化アンモニウムまたは塩化亜鉛を主体としたものがあ
った。前者に比べ後者は、重負荷放電特性が優れている
ので一般Ｃユ賞用されていた。しかし、最近はより高温
貯蔵特性の優れた電池が要望されるよう（ユなってきた
が、いまだそれζユは応えられていなかった。"Conventional technology" Conventional manganese drying 1! The pond contains a positive electrode active substance 1 manganese dioxide, a negative electrode active substance (zinc), acetylene black as a conductive aid and electrolyte retaining material, and an electrolyte mainly containing zinc chloride, ammonium chloride, or zinc chloride. Compared to the former, the latter had superior heavy-load discharge characteristics and was generally used as a battery.However, recently there has been a demand for batteries with better high-temperature storage characteristics. I still haven't been able to answer that question.
［発明が解決しよりとする問題点」
マンガン乾電池の放電特性は、正極合剤の配合組成によ
ってほぼ決定される。そして配合成分の正極作用物質で
ある二酸化マンガン、導電補助付兼電解液保持材である
アセチレンブラック及び電解液の比率は、おのずとある
範囲内に収まってくる。[Problems to be solved by the invention] The discharge characteristics of a manganese dry battery are almost determined by the composition of the positive electrode mixture. The ratio of the compounded components of manganese dioxide which is a positive electrode active substance, acetylene black which is a conductive aid and electrolyte holding material, and electrolyte solution naturally falls within a certain range.
重負荷放電特性を良くしようとして電解液の比率が多い
正極合剤で乾電池を作ると、製造直後の性能は向上する
が、高温（６０℃）貯蔵すると劣下率が大きく、逆に電
解液の比率が少ない正極合剤で作った乾電池より悪くな
ってしまった。If a dry battery is made using a positive electrode mix with a high proportion of electrolyte in order to improve heavy-load discharge characteristics, the performance immediately after manufacture will improve, but if stored at high temperatures (60°C), the rate of deterioration will be large, and conversely, the electrolyte will deteriorate. It was worse than a battery made with a positive electrode mix with a lower ratio.
この原因は、品温貯蔵中に正極合剤中の水分が僅かすっ
であるが蒸発して、正極合剤上部が収縮し正極合剤とセ
パレーターとの間に空隙が生じ、それによって乾゛直池
の反応面精を減少させるためである。この現象は、電解
液量が正極合剤の組成では保持能力の限界に近い程顕著
であった。The cause of this is that a small amount of water in the positive electrode mixture evaporates during storage at the same temperature, causing the upper part of the positive electrode mixture to shrink and creating a gap between the positive electrode mixture and the separator, which causes the drying process to occur quickly. This is to reduce the reaction stress of the pond. This phenomenon was more pronounced as the amount of electrolyte approached the limit of the holding capacity of the positive electrode mixture composition.
また、正極作用物質の二酸化マンガンと導電補助付兼電
解液保持材のアセチレンブラックとの高温貯蔵中での反
応（ユよりＣＯ２が発生し、やはり前記と同様に正極合
斧］とセパレーターとの蘭Ｃ二空［が生じ反応面積を減
少させ、高温貯蔵後の重負荷放電特性を悪くしていた。In addition, the reaction between manganese dioxide, which is a positive electrode active material, and acetylene black, which is a conductive agent and electrolyte holding material, during high-temperature storage (CO2 is generated from the yellow, and the positive electrode mixture is similar to the above), and the reaction between the separator and the separator. C divacancies were generated, reducing the reaction area and worsening the heavy load discharge characteristics after high temperature storage.
本発明は上記の問題を軽減し、高温貯蔵性（ユ優ね？マ
ンガン乾電池を提供するものである。The present invention alleviates the above problems and provides a manganese dry battery that can be stored at high temperatures.
「間給点を解決Ｔ；！まための手段」
本発明者は前記の問題を軽減させるため、正極作用物質
として化学二酸化マンガンに着目し、電解液保持能力と
ガス発生量を調べた。この化学二酸化マンガンは、粗粒
天然二酸化マンガンを焙焼１、 ｈｌｎ ２．０３とし
、硫酸中（二浸漬しＭｎＯ２とし、中和乾燥後プレスし
てタップ密度を１．６〜２．３ ？／ｃＡ ｌニし念も
のである（以下活性化二酸化マンガンと言う）。"A Means to Solve the Intermediate Supply Point" In order to alleviate the above-mentioned problems, the present inventors focused on chemical manganese dioxide as a positive electrode active material and investigated its electrolyte holding capacity and gas generation amount. This chemical manganese dioxide is made by roasting coarse grained natural manganese dioxide to HLN 2.03, immersing it in sulfuric acid (2) to make MnO2, neutralizing and drying it, then pressing it to a tap density of 1.6 to 2.3?/ cAl (hereinafter referred to as activated manganese dioxide).
タップ密度と電解液保持能力及びガス発生量との関係は
表１の通りでめった。The relationship between tap density, electrolyte holding capacity, and gas generation amount is shown in Table 1.
注１）電解液保持能力は、各タップ密度の活性化二酸化
マンガン２０．Ｏｆを三角プレス：＋５ＱＱｒｒｕ（二
人れ、界面活性剤入りの水を滴下し振り混ぜ、二酸化マ
ンガンが一つの団塊；−なった時の滴下量（ｍｌ）を、
電解液保持能力とした。この特性は、電池製造上の作業
性や他の放電特性などから３．８〜４．８ ｒｒＬＪ−
が適している。Note 1) The electrolyte holding capacity is 20% of the activated manganese dioxide for each tap density. Of triangle press: +5QQrru (Both people, drop water containing surfactant and shake to mix. When manganese dioxide becomes one lump; -, the amount of dripping (ml) is,
It was defined as the electrolyte holding capacity. This characteristic is 3.8 to 4.8 rrLJ- due to workability in battery manufacturing and other discharge characteristics.
is suitable.
２）ガス発生量は、各タップ密度の活性化二酸化マンガ
ン５０２とアセチレンブラック１．０２と′電解液（Ｚ
ｎＣＪ−２２５〜■／Ｗ％、 ＮＨ４ｅｘ ２．５Ｗ
／Ｗ％）３．４ｍｆとで正極合剤を調製し、それをガス
発生測定容器の中１−人ね、６０°Ｃで１０日間貯貯蔵
発生したガス量を測定した。このガス発生量が少ないほ
ど良い。2) The amount of gas generated is determined by the amount of activated manganese dioxide 502, acetylene black 1.02, and electrolyte (Z) of each tap density.
nCJ-225~■/W%, NH4ex 2.5W
/W%) 3.4mf, and stored it in a gas generation measurement container for 10 days at 60°C to measure the amount of gas generated. The smaller the amount of gas generated, the better.
土肥の試験イニよ番）、活性化二酸化マンガンのタップ
密度は、１．６〜２．３ ｆ’／ｌｒｉのものが良いこ
とがわかる。According to Doi's test results, activated manganese dioxide has a tap density of 1.6 to 2.3 f'/lri.
また、導電補助付兼電解液保持材のアセチレンブラック
よりガス発生量が少ないと言われている。It is also said to produce less gas than acetylene black, which is a conductive aid and electrolyte holding material.
石油を一部酸化して作られたカーボンブラックについて
ガス発生量を調べた。試験方法は前記の活性化二酸化マ
ンガンのガス発生量の測定と同じように行い、二酸化マ
ンガンにはタップ密度１．８Ｐ／ｍの活性化二酸化マン
ガンと市販の電解二酸化マンガンを用い、カーボンブラ
ック（二はアセチレンブラックと石油から作られたカー
ボンブラックを用い、それぞねを組合せた正極合剤を調
製しガス発生量を測定した。その結果を表２（＝示す。We investigated the amount of gas generated from carbon black made by partially oxidizing petroleum. The test method was the same as the measurement of the amount of gas generated from activated manganese dioxide, using activated manganese dioxide with a tap density of 1.8P/m and commercially available electrolytic manganese dioxide, and carbon black (dioxide). used acetylene black and carbon black made from petroleum to prepare a positive electrode mixture that was a combination of each, and measured the amount of gas generated.The results are shown in Table 2 (=).
表２
以上の二つの試験結果から、正極作用物質としてはタッ
プ密度１．６〜２．３？／ｃ−の活性化二酸化マンガン
、導電補助材ｎｔ解液液保持材しては石油の一部酸化（
二よって作られたカーボンブラックが、ガス発生量の少
ないものであることがわかった。Table 2 From the above two test results, the tap density is 1.6 to 2.3 as a positive electrode active substance. /c- activated manganese dioxide, conductive auxiliary material nt solution retaining material is partially oxidized petroleum (
It was found that the carbon black produced by the above method produced a small amount of gas.
こねらを用いて製造したマンガン乾電池は、高温貯蔵性
が優れたものであることが予想される。It is expected that manganese dry batteries manufactured using Konera will have excellent high-temperature storage properties.
［実施例］
実施例１
活性化二酸化マンガン６０重量部１石油から作ったカー
ボンブラック１２重量部及び酸化亜鉛３重量部とをよく
混合し、電解液（ＺｎＣ１２２５Ｗ／ＡＶ％、ＮＨ４Ｃ
：ｊ２．５ｖ！／ｗ％）５３重量部加え混合し、均一な
正極合剤を調製した。°この正極合剤を用いてＲ２０形
マンガン乾電池を製造した。この乾電池を６０℃に１０
日。[Example] Example 1 60 parts by weight of activated manganese dioxide, 12 parts by weight of carbon black made from petroleum, and 3 parts by weight of zinc oxide were mixed well, and electrolyte solution (ZnC1225W/AV%, NH4C
:j2.5v! /w%) was added and mixed to prepare a uniform positive electrode mixture. °An R20 type manganese dry battery was manufactured using this positive electrode mixture. This battery was heated to 60℃ for 10
Day.
２０日及び４０日間貯蔵し、２Ω連続放電試験を行った
。試験結果は、６０℃貯蔵前電池１００個の放電持続時
間（終止電圧０．９Ｖ）の平均値を１００とした場合の
、各貯蔵後転電池１００個の放電持続時間の平均値とし
て表３に示した。The samples were stored for 20 and 40 days and subjected to a 2Ω continuous discharge test. The test results are shown in Table 3 as the average value of the discharge duration of 100 batteries after each storage, where the average value of the discharge duration (end voltage 0.9V) of 100 batteries before storage at 60°C is set as 100. Indicated.
比較例１
実施例１の活性化二酸化マンガンを・市販′ｆｊ１Ｍ二
酸化マンガンに換えたほかは、実施例１とまったく同様
（ユ試験し、その結果を表ＩＣ−示した。Comparative Example 1 A test was carried out in exactly the same manner as in Example 1, except that the activated manganese dioxide in Example 1 was replaced with commercially available fj1M manganese dioxide.The results are shown in Table IC.
比較例２
実施例１の石油から作ったカーボンブラックを市販のア
セチレンブラック（＝換えたほかは、実施例１とまった
く同様Ｃ：試験し、その結果を表３に示した。Comparative Example 2 The carbon black made from petroleum in Example 1 was replaced with commercially available acetylene black (C: Test was conducted in exactly the same manner as in Example 1, except that it was replaced with commercially available acetylene black), and the results are shown in Table 3.
比較例３
実施例１の活性化二酸化マンガンを市販の電解二酸化マ
ンガンに、石油から作ったカーボンブラックを市販のア
セチレンブラック（：換えたほかは、実施例１とまった
く同様Ｃ−試験し、その結果を表３Ｃ二示した。Comparative Example 3 A C-test was conducted in exactly the same manner as in Example 1, except that the activated manganese dioxide in Example 1 was replaced with commercially available electrolytic manganese dioxide, and the carbon black made from petroleum was replaced with commercially available acetylene black (:). is shown in Table 3C.
表３
また、活性化二酸化マンガンのタップ密度と電池放電特
性との関係を調べた。実験は実施例１と同様（；行った
。但し、乾電池與造の作業性から、タップ密度が１．８
？／ｃｒｌ より小さい活性化二酸化マンガン（二は
電解液を多口に、太きいものには少な目Ｃ：加え正極合
剤（−シた。試験は放電持続時間比のほかに、バラツキ
幅も測定し、表４（ユ示し念。Table 3 We also investigated the relationship between the tap density of activated manganese dioxide and battery discharge characteristics. The experiment was carried out in the same manner as in Example 1.However, due to the workability of manufacturing dry batteries, the tap density was 1.8.
? /crl Smaller activated manganese dioxide (2: Add a large amount of electrolyte, C: Add a small amount of electrolyte to a larger one. Add positive electrode mixture (-). In addition to the discharge duration ratio, the test also measured the variation width. , Table 4 (Yu Shinmyo).
以下余白
［発明の効果］
以上のように、本発明は天然二酸化マンガンの焙焼物で
あるＭｎ２Ｏ８を硫酸溶液Ｃユ浸漬しλ１ｎ０２１ユし
て水洗乾燥後、プレスしてタップ密度を大きくした化学
二酸化マンガンと石油を一部酸化することによって作ら
れたカーボンブラックを導電補助液保持材としたことに
よって、従来電池で得られなかった高温貯蔵特性が優れ
、工業的価値極めて犬な２）ものである。Margins below [Effects of the Invention] As described above, the present invention is a chemical manganese dioxide obtained by soaking Mn2O8, which is a roasted product of natural manganese dioxide, in a sulfuric acid solution, washing it with water, drying it, and pressing it to increase the tap density. By using carbon black, which is made by partially oxidizing petroleum and petroleum, as the conductive auxiliary liquid holding material, it has excellent high-temperature storage characteristics that could not be obtained with conventional batteries, and has extremely high industrial value.
Claims (2)
８を、硫酸溶液に浸漬しＭｎＯ＿２にして水洗乾燥後、
プレスしてタップ密度を大きくした化学二酸化マンガン
からなる正極作用物質と、石油を一部酸化することによ
って作られたカーボンブラックを導電補助付兼電解液保
持材としたことを特徴とするマンガン乾電池。(1) Mn_2O_ which is a roasted product of natural manganese dioxide
8 was immersed in a sulfuric acid solution, converted to MnO_2, washed with water, and dried.
A manganese dry battery characterized by using a positive electrode material made of chemical manganese dioxide which has been pressed to increase the tap density, and carbon black made by partially oxidizing petroleum as a conductive aid and an electrolyte retaining material.
２．３ｇ／ｃｍ＾３であることを特徴とする特許請求の
範囲第１項記載のマンガン乾電池。(2) The tap density of the chemical manganese dioxide is 1.6 to
The manganese dry battery according to claim 1, characterized in that it has a density of 2.3 g/cm^3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60261349A JPS62122060A (en) | 1985-11-22 | 1985-11-22 | Manganese dry battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60261349A JPS62122060A (en) | 1985-11-22 | 1985-11-22 | Manganese dry battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62122060A true JPS62122060A (en) | 1987-06-03 |
Family
ID=17360602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60261349A Expired - Lifetime JPS62122060A (en) | 1985-11-22 | 1985-11-22 | Manganese dry battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62122060A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6448368A (en) * | 1987-08-18 | 1989-02-22 | Toshiba Battery | Manganese dry element cell |
| JP2009040509A (en) * | 2008-11-26 | 2009-02-26 | Dainippon Printing Co Ltd | Easily openable packaging bag |
-
1985
- 1985-11-22 JP JP60261349A patent/JPS62122060A/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6448368A (en) * | 1987-08-18 | 1989-02-22 | Toshiba Battery | Manganese dry element cell |
| JP2009040509A (en) * | 2008-11-26 | 2009-02-26 | Dainippon Printing Co Ltd | Easily openable packaging bag |
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