JPH0261096B2 - - Google Patents
Info
- Publication number
- JPH0261096B2 JPH0261096B2 JP56212816A JP21281681A JPH0261096B2 JP H0261096 B2 JPH0261096 B2 JP H0261096B2 JP 56212816 A JP56212816 A JP 56212816A JP 21281681 A JP21281681 A JP 21281681A JP H0261096 B2 JPH0261096 B2 JP H0261096B2
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- positive electrode
- manganese
- catalyst layer
- mnox
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 11
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 11
- 229910016978 MnOx Inorganic materials 0.000 claims description 5
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910003174 MnOOH Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RTBHLGSMKCPLCQ-UHFFFAOYSA-N [Mn].OOO Chemical compound [Mn].OOO RTBHLGSMKCPLCQ-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Description
【発明の詳細な説明】
本発明は活性炭とMnOxのＸ値が1.6〜1.63であ
るマンガン酸化物とを主体とする触媒層を空気電
池の正極に使用することにより、放電特性、保存
性能にすぐれた空気電池を提供することを目的と
する。[Detailed Description of the Invention] The present invention provides excellent discharge characteristics and storage performance by using a catalyst layer mainly composed of activated carbon and manganese oxide with an MnOx X value of 1.6 to 1.63 for the positive electrode of an air battery. The purpose of this research is to provide an air battery with improved performance.
従来、空気電池の触媒層としては種々のものが
検討されてきている。白金属元素や銀などの貴金
属を活性炭に析出させたもの、活性炭と二酸化マ
ンガンを混合したもの、活性炭とコバルトフタロ
シアニンとの混合物、あるいはその熱処理品など
を触媒層に用いることが提案されている。一般
に、白金属元素、銀などの触媒効果は大きいが、
現状、補聴器用として注目されているボタン型空
気電池に貴金属触媒を使用することは一次電池が
一般に再生、再使用し難い点を考慮すると、高価
なものとなる。この為安価な二酸化マンガンを空
気電池用触媒にすることが過去から種々考えられ
ているが、初度の開路電圧を高くすることに効果
は示すものの、放電電圧を高めるには必ずしも十
分でなかつた。 Conventionally, various catalyst layers for air batteries have been studied. It has been proposed to use for the catalyst layer a material in which precious metals such as platinum metal elements and silver are precipitated on activated carbon, a mixture of activated carbon and manganese dioxide, a mixture of activated carbon and cobalt phthalocyanine, or heat-treated products thereof. In general, platinum metal elements, silver, etc. have a large catalytic effect, but
Currently, the use of precious metal catalysts in button-type air batteries, which are attracting attention for use in hearing aids, is expensive, considering that primary batteries are generally difficult to reproduce and reuse. For this reason, various attempts have been made in the past to use inexpensive manganese dioxide as a catalyst for air batteries, but although this has been effective in increasing the initial open circuit voltage, it has not necessarily been sufficient to increase the discharge voltage.
本発明はMnOxであらわされるマンガン酸化物
のうち、Ｘ値が1.60〜1.63のものを活性炭と併用
することにより、酸素極として触媒能の高い正極
を用いた空気電池を提供することにある。 The object of the present invention is to provide an air battery using a positive electrode with high catalytic ability as an oxygen electrode by using a manganese oxide represented by MnOx with an X value of 1.60 to 1.63 in combination with activated carbon.
以下実施例より詳述する。 This will be explained in more detail in Examples below.
MnOxのうちＸ値が1.60〜1.63のマンガン酸化
物は次のようにし製造される。硫酸マンガン溶液
に過酸化水素を加えこれにアンモニア水を加える
と、オキシ水酸化マンガン（MnOOH）が沈でん
する。これを濾過、水洗、濾過を行ないMnOOH
をつくる。このMnOOHを窒素雰囲気中で270〜
320℃で熱処理すると、MnO1.6〜MnO1.63のマン
ガン酸化物が得られる。このマンガン酸化物45
部、導電材として炭素粉末10部、活性炭25部、四
フツ化エチレン20部にスラリー状になるよう水を
添加して混練し、これをニツケル網に塗着、充填
後、乾燥して所定の大きさに打ち抜き、正極とし
た。この正極触媒を用いて第１図に示す構造で大
きさがR44サイズのボタン型空気電池を作製し
た。 Among MnOx, manganese oxide having an X value of 1.60 to 1.63 is produced as follows. When hydrogen peroxide is added to a manganese sulfate solution and ammonia water is added to this, manganese oxyhydroxide (MnOOH) precipitates. This is filtered, washed with water, and filtered to produce MnOOH.
Create. This MnOOH is 270 ~
Heat treatment at 320°C yields manganese oxides of MnO 1.6 to MnO 1.63 . This manganese oxide 45
10 parts of carbon powder, 25 parts of activated carbon, and 20 parts of polytetrafluoroethylene as conductive materials are mixed with water to form a slurry, applied to a nickel mesh, filled, dried, and formed into the specified shape. It was punched out to size and used as a positive electrode. Using this positive electrode catalyst, a button-type air battery having the structure shown in FIG. 1 and having a size of R44 was produced.
本発明の電池をＡ、同様な処方製法で得られた
従来の二酸化マンガンと活性炭とからなる正極触
媒層をもつ電流をＢとし、180Ω連続放電の初度
と、45℃３ケ月保存後の結果をそれぞれ第２図、
第３図に示した。 The battery of the present invention is A, and the current with a conventional cathode catalyst layer made of manganese dioxide and activated carbon obtained by a similar manufacturing method is B. Figure 2, respectively.
It is shown in Figure 3.
これらの結果から明らかなようにＡは放電特
性、貯蔵性に極めてすぐれていることがわかる。
このようなMnOxのＸ値が1.60〜1.63のものが、
触媒としてすぐれている理由はさだかでないが、
二酸化マンガンの場合は、放電又は保存中に浸透
する電解液の存在下で正極触媒層中の二酸化マン
ガンと活性炭との間で電気化学反応が生じ、この
二酸化マンガン反応物の触媒能が低いことに起因
するものと考えられる。 As is clear from these results, it can be seen that A has extremely excellent discharge characteristics and storage properties.
Such MnOx with an X value of 1.60 to 1.63 is
There are many reasons why it is excellent as a catalyst, but
In the case of manganese dioxide, an electrochemical reaction occurs between manganese dioxide and activated carbon in the positive electrode catalyst layer in the presence of an electrolyte that permeates during discharge or storage, resulting in the low catalytic ability of this manganese dioxide reactant. This is thought to be due to this.
なおMnO1.60〜1.63のＸ値のうち、Mn5O8
（MnO1.6）は代表的な化合物である。 Of the X values of MnO 1.60 to 1.63 , Mn 5 O 8
(MnO 1.6 ) is a typical compound.
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、第３図は放電特性を示す
図である。
１……正極触媒層、２……正極集電体（ニツケ
ル網）、３……負極亜鉛、４……セパレータ、５
……正極容器、６……負極容器、７……ガスケツ
ト、８……支持体紙、９……空気孔。
FIG. 1 is a sectional view of a button-type air cell according to an embodiment of the present invention, and FIGS. 2 and 3 are diagrams showing discharge characteristics. 1... Positive electrode catalyst layer, 2... Positive electrode current collector (nickel mesh), 3... Negative electrode zinc, 4... Separator, 5
... Positive electrode container, 6 ... Negative electrode container, 7 ... Gasket, 8 ... Support paper, 9 ... Air hole.
Claims (1)
物と活性炭を主体とする触媒層を正極に備えたこ
とを特徴とする空気電池。1. An air cell characterized in that the positive electrode is equipped with a catalyst layer mainly composed of manganese oxide and activated carbon, the X value of MnOx being 1.6 to 1.63.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56212816A JPS58117648A (en) | 1981-12-29 | 1981-12-29 | Air cell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56212816A JPS58117648A (en) | 1981-12-29 | 1981-12-29 | Air cell |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58117648A JPS58117648A (en) | 1983-07-13 |
| JPH0261096B2 true JPH0261096B2 (en) | 1990-12-19 |
Family
ID=16628829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56212816A Granted JPS58117648A (en) | 1981-12-29 | 1981-12-29 | Air cell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58117648A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59171468A (en) * | 1983-03-18 | 1984-09-27 | Matsushita Electric Ind Co Ltd | Air pole and manufacture of its catalyzer |
| US6127061A (en) * | 1999-01-26 | 2000-10-03 | High-Density Energy, Inc. | Catalytic air cathode for air-metal batteries |
-
1981
- 1981-12-29 JP JP56212816A patent/JPS58117648A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58117648A (en) | 1983-07-13 |
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