JPS58157068A - Button-type air cell - Google Patents
Button-type air cellInfo
- Publication number
- JPS58157068A JPS58157068A JP57041264A JP4126482A JPS58157068A JP S58157068 A JPS58157068 A JP S58157068A JP 57041264 A JP57041264 A JP 57041264A JP 4126482 A JP4126482 A JP 4126482A JP S58157068 A JPS58157068 A JP S58157068A
- Authority
- JP
- Japan
- Prior art keywords
- button
- type air
- manganese
- manganese dioxide
- 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.)
- Pending
Links
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 229910002804 graphite Inorganic materials 0.000 abstract description 3
- 239000010439 graphite Substances 0.000 abstract description 3
- 238000004321 preservation Methods 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 3
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Hybrid Cells (AREA)
Abstract
Description
【発明の詳細な説明】
本発明はボタン型空気電池に用いらｎている正極触媒中
に結晶相の異なる二酸化マンガンを添加することによっ
て、空気孔を４がｎている保存状態時の開路電圧の安定
化をはかることを目的としたものである。DETAILED DESCRIPTION OF THE INVENTION The present invention has been developed by adding manganese dioxide having different crystal phases to the positive electrode catalyst used in button-type air batteries, thereby increasing the open circuit voltage during storage when the air pores are The purpose is to stabilize the
ボタン型空気電池の正極触媒の反応は、０２＋ｆ（２０
＋２ｅ−０２Ｈ”−＋ＯＨ””−−−−−６）弐〇２Ｈ
”−＋ＯＨ″’＋２Ｈ−ｆ（２０２＋Ｈ２０・・・・・
（２）式Ｈ２Ｏ２→−４−０２＋Ｈ２ｏ ・・
・・・ （３）式で表わさｎる。通常、触媒能は３
式に律速さ在るこの触媒能を上げるために活性炭、マン
ガン酸化物、例えば三二酸化マンガン、及び黒鉛等の導
電材の三成分を主とし、こ扛に撲水性結着剤としてフッ
素系樹脂を加えたものを集電体に塗着し、所定のサイズ
に打ち抜いて正極触媒（空気１傘）としていた。The reaction of the positive electrode catalyst of a button-type air cell is 02+f(20
+2e-02H"-+OH""------6) 2〇2H
"-+OH"'+2H-f (202+H20...
(2) Formula H2O2→-4-02+H2o...
... Expressed by equation (3). Usually the catalytic capacity is 3
In order to increase this catalytic ability, which is rate-determining in the formula, the three main components are activated carbon, manganese oxide, such as manganese sesquioxide, and a conductive material such as graphite. The added material was applied to a current collector and punched out to a predetermined size to form a positive electrode catalyst (one umbrella of air).
ところが、この正極触媒を用いたボタン型空気電池の空
気孔をシール紙等で塞いで保存すると、開路電圧は０．
９ｖ〜１．２８Ｖまで低下した。従って保存者において
電圧を確認するとバラツキが大きく、その電池が正常で
あるか否かは全くわからない状態であった。However, if a button-type air battery using this cathode catalyst is stored with the air hole covered with sticker paper, etc., the open circuit voltage will be 0.
It decreased to 9v to 1.28V. Therefore, when the conservator checked the voltage, there was a large variation, and it was completely unclear whether the battery was normal or not.
本発明は、三二酸化マンガンを含む正極触媒中に結晶相
の異なる二酸化マンガンを混入することで保存時の開路
電圧の安定化を図ったものである。The present invention attempts to stabilize the open circuit voltage during storage by mixing manganese dioxide having different crystal phases into a positive electrode catalyst containing manganese sesquioxide.
以下、本発明の実施についてＲ４４サイズのボタン型空
気電池（直径１１ 、６１Ｍｎ ＊高さ５．４閣、公称
容量４ｏｏｍＡｈ）を例に説明する。Hereinafter, the implementation of the present invention will be explained using an R44 size button air battery (diameter 11, 61Mn * height 5.4cm, nominal capacity 4oomAh) as an example.
第１図は上記電池の部分断面図を示し、図中１は正極ケ
ースでケース底面に凸部をそなえ、空気孔２を有してい
る。３は空気拡散紙、４はフッ素電性を持たせるための
黒鉛、史に触媒能を上げるために三二酸化マンガン（１
Ｖｉｎ ２０３ ） ｋ混合しこｎに更に結晶相の異な
る例えばγＩａＳβ、δ型の二酸化マンガンを単独もし
くは２成分以上の混合物とし加え、−４成分もしくはそ
扛以上の成分とする。この時二酸化マンガンの添加量と
しては、三二酸化マンガン１００部に対して菫量比で１
０〜６ｏ部を添加するのか最もよい。この理由としては
１０部以下にした時、均一混合性に欠けるため、無添加
の場合保存後の開路電圧は０．９８〜１．２８Ｖに対し
て１．２６〜１．３２Ｖと幾分電圧安定化効果はできる
もののバラツキが大きい。又、６０部以上では添加する
二酸化マンガンの電位がそのまま電池電圧に影響し、１
．３８０〜１．４１２Ｖにまで上がり、バラツキが大き
いと共にこの電池’ＩｅｏＣで保存すると約２０日で１
．３２〜１，３６Ｖと更に不安定なものとなる。この電
位低下は二酸化マンガンが自己放電さ扛るために起こる
ものである。FIG. 1 shows a partial cross-sectional view of the above-mentioned battery, and in the figure, 1 is a positive electrode case, which has a convex portion on the bottom surface of the case and has an air hole 2. 3 is air diffusion paper, 4 is graphite to give it fluorine charge, and manganese sesquioxide (1
Vin 203) Further, manganese dioxide having a different crystal phase, for example, γIaSβ, δ type, is added alone or as a mixture of two or more components to the k mixed mixture to form a -4 component or a mixture of two or more components. At this time, the amount of manganese dioxide added is 1 in violet ratio to 100 parts of manganese sesquioxide.
It is best to add 0 to 6 parts. The reason for this is that when the amount is 10 parts or less, uniform mixing is lacking, so the open circuit voltage after storage is 1.26 to 1.32V, which is somewhat stable compared to 0.98 to 1.28V in the case of no additives. Although it has a positive effect, it varies widely. In addition, if it is more than 60 parts, the potential of the added manganese dioxide directly affects the battery voltage, and 1
．． The voltage rises to 380 to 1.412V, and there is a large variation, and when stored with this battery 'IeoC, it loses 1V in about 20 days.
．． It becomes even more unstable at 32 to 1,36V. This potential drop occurs because manganese dioxide undergoes self-discharge.
しかし前記１０〜６０部の添加範囲では前述のような現
象は比較的少なく、その保存後の電圧も極めて安定して
いる。ここではγ型ニポ化マンガンを３ｏ部添加したも
のを用いた。However, within the addition range of 10 to 60 parts, the above-mentioned phenomenon is relatively rare, and the voltage after storage is also extremely stable. Here, a material to which 30 parts of γ-type manganese nipide was added was used.
なお、６はセパレータ、７は電解液含浸材をな−す不織
布、８はナイロンよりなるガスケット、９飽和したもの
を用いｆｃ。In addition, 6 is a separator, 7 is a nonwoven fabric which is an electrolyte-impregnated material, 8 is a gasket made of nylon, and 9 is a saturated one.
次に本発明による正極触媒構成（Ａ）と、二酸化マンガ
ンを加えない従来の正極触ｄｍ成〔Ｂ〕とについて各々
電池を楕成し、空気孔を基いだ状態でａｏＣ保存を行な
った。第２図に保存日数と電池電圧との関係推移を示し
た。その結４：ｅｏｃテ２０８４Ｖ存ＱＩＫ （Ｂ ）
ｉｊ’ｉ？Ｊ期１．４１〜１．４５ Ｖあった開路電
圧が０．９〜１，２８Ｖに低下し、かつそのバラツキも
極めて大きくなる。Next, batteries were formed using the cathode catalyst structure (A) according to the present invention and the conventional cathode catalyst structure [B] in which no manganese dioxide was added, and aoC storage was performed using air holes. Figure 2 shows the relationship between storage days and battery voltage. Conclusion 4: eocte 2084V existence QIK (B)
ij'i? The open circuit voltage, which was 1.41 to 1.45 V during the J period, drops to 0.9 to 1.28 V, and the variation thereof becomes extremely large.
一方、本発明の信成では初期１．３６〜１．３８Ｖであ
ったものが２０日保存後でも１．３２〜１．、３４Ｖに
なり、かつそのバラツキも極めて小さい。On the other hand, in the Shinsei of the present invention, the initial voltage was 1.36 to 1.38V, but even after 20 days of storage, it was 1.32 to 1. , 34V, and its variation is extremely small.
従って、その電池が保存後も正常であるかどうかはシー
ル紙を一々はがさなくても電圧を測定す扛ば明らかにな
り、実用上の利点は極めて大きいものである。Therefore, whether or not the battery is in good condition after storage can be determined by measuring the voltage without having to remove each sticker, which is a great practical advantage.
第１図は本発明の実施例におけるボタン型空気電池の断
面図、第２図は保存と開路′電圧との関系推移を示す図
である。
１・・・−・正極ケース、２・・・・・空気孔、５・・
・・正極触媒、１０・・・・・・亜鉛負極。
代理人の氏名 弁理士 中 尾 敏 男 ほか１名（Ａ
）ＴＩ、 奮 四
−３トFIG. 1 is a sectional view of a button-type air cell according to an embodiment of the present invention, and FIG. 2 is a diagram showing the relationship between storage and open circuit voltage. 1...--Positive electrode case, 2...Air hole, 5...
...Positive electrode catalyst, 10...Zinc negative electrode. Name of agent: Patent attorney Toshio Nakao and one other person (A
) TI, 4-3
Claims (3)
た正極触媒と、亜鉛負極と、アルカリ電解液とを備えた
ボタン型空気電池であって、前記正極触媒中に結晶相の
異なる二酸化マンガンを１種あるいはそれ以上混入して
なることを特徴としたボタン型空気電池。(1) A button-type air battery comprising a positive electrode catalyst mainly composed of activated carbon, manganese sesquioxide, and a conductive material, a zinc negative electrode, and an alkaline electrolyte, wherein the positive electrode catalyst contains manganese dioxide having different crystal phases. A button-type air battery containing one or more types of.
、ａ型、β型及びδ型のいず扛かである特許請求の範囲
第１項に記載のボタン型空気電池。(2) The button-type air battery according to claim 1, wherein the manganese dioxide mixed in the positive electrode catalyst is one of γ type, a type, β type, and δ type.
量とビで三二酸化マンガン１００部当り１０〜６０部で
ある特許請求の範囲第１項又は第２項記載のボタン型空
気電池。(3) The button-type air battery according to claim 1 or 2, wherein the amount of manganese dioxide mixed into the positive electrode catalyst is 10 to 60 parts by weight and bicarbonate per 100 parts of manganese sesquioxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57041264A JPS58157068A (en) | 1982-03-15 | 1982-03-15 | Button-type air cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57041264A JPS58157068A (en) | 1982-03-15 | 1982-03-15 | Button-type air cell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58157068A true JPS58157068A (en) | 1983-09-19 |
Family
ID=12603586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57041264A Pending JPS58157068A (en) | 1982-03-15 | 1982-03-15 | Button-type air cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58157068A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4595643A (en) * | 1983-03-18 | 1986-06-17 | Matsushita Electrical Industrial Co., Ltd. | Air cell electrode and process for preparing its catalyst |
-
1982
- 1982-03-15 JP JP57041264A patent/JPS58157068A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4595643A (en) * | 1983-03-18 | 1986-06-17 | Matsushita Electrical Industrial Co., Ltd. | Air cell electrode and process for preparing its catalyst |
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