JPS5924494B2 - Manufacturing method of positive electrode for silver oxide batteries - Google Patents
Manufacturing method of positive electrode for silver oxide batteriesInfo
- Publication number
- JPS5924494B2 JPS5924494B2 JP12576276A JP12576276A JPS5924494B2 JP S5924494 B2 JPS5924494 B2 JP S5924494B2 JP 12576276 A JP12576276 A JP 12576276A JP 12576276 A JP12576276 A JP 12576276A JP S5924494 B2 JPS5924494 B2 JP S5924494B2
- Authority
- JP
- Japan
- Prior art keywords
- silver oxide
- ago
- positive electrode
- manufacturing
- oxide batteries
- 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
Links
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 title claims description 16
- 229910001923 silver oxide Inorganic materials 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 22
- 235000019441 ethanol Nutrition 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- Y02E60/12—
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Description
【発明の詳細な説明】
現在、電卓、カメラ、時計等の小型電子機器の電力源と
して、水銀電池、酸化銀電池が使用されているが、最近
、電子技術の進歩により、半導体の使用が増加してくる
につれて高電圧、高街力の電池が要求されている。[Detailed Description of the Invention] Currently, mercury batteries and silver oxide batteries are used as power sources for small electronic devices such as calculators, cameras, and watches, but with recent advances in electronic technology, the use of semiconductors has increased. As the technology advances, batteries with higher voltage and higher power are required.
そこで、最近注目されているものに二価酸化銀ＡｇＯを
正極活物質に使用した電池がある。このＡｇＯは一価酸
化銀Ａｇ２Ｏ活物質に対して、重量当たりの容量で１．
８６倍、容積当たりの容量で１．９３倍の大容量を取り
出す事ができる。しかし、このＡｇ０は、アルカリ溶液
中において不安定であり、特に高温になると分解して酸
素を発生する。２ＡｇＯ→Ａｇ２Ｏ＋ιＯ２
このように、二価酸化銀よりー価酸化銀に分解する時の
酸素発生により電池の内圧を上昇させるので、密閉型電
池に使用できないという問題点があつた。Therefore, a battery that uses divalent silver oxide AgO as a positive electrode active material has recently attracted attention. This AgO has a capacity per weight of 1.0% relative to the monovalent silver oxide Ag2O active material.
It is possible to take out 86 times the capacity and 1.93 times the capacity per volume. However, this Ag0 is unstable in an alkaline solution and decomposes to generate oxygen especially at high temperatures. 2AgO→Ag2O+ιO2 As described above, the internal pressure of the battery increases due to the generation of oxygen when divalent silver oxide is decomposed into -valent silver oxide, so there was a problem that it could not be used in a sealed battery.
そこで、安定したＡｇ０を得るため種々検討されている
。Therefore, various studies have been made to obtain stable Ag0.
例えば、アルカリ溶液中の銀塩の陽極酸化、または硝酸
銀溶液の電気分解、あるいは銀塩のオゾン酸化等の製造
方法が提案されているが、現在のところ、密閉型電池と
して実用可能なＡｇＯの製造法は確立されていない。本
発明は、ＡｇＯを一般式ＣｎＨ２ｎＨＯＨ（ただしｎ＝
３〜１０）で表さわるアルコールで還元することで安定
化させ、不安定なＡｇＯの分解にもとづくガス発生を効
果的に抑制しうることを見出したことに基つくものであ
る。For example, production methods such as anodic oxidation of silver salt in an alkaline solution, electrolysis of silver nitrate solution, or ozone oxidation of silver salt have been proposed, but at present, the production of AgO that can be used practically as a sealed battery has been proposed. No law has been established. The present invention uses AgO with the general formula CnH2nHOH (where n=
This is based on the discovery that the gas generation caused by the decomposition of unstable AgO can be effectively suppressed by stabilizing it by reducing it with the alcohols represented by 3 to 10).
ＡｇＯの製造においては、一般的に安定なＡｇ０と不安
定なＡｇＯが混合した状態で得られるものと考えられて
おり、ＡｇＯｘで表した場合、ｘの値が０．９〜１．０
の範囲が最も安定であり、通常のＡｇ０はＸが１．０以
上にある。In the production of AgO, it is generally thought that a mixture of stable Ag0 and unstable AgO is obtained, and when expressed as AgOx, the value of x is 0.9 to 1.0.
The range of X is the most stable, and normal Ag0 has X of 1.0 or more.
本発明は主としてＸが１．０以上の不安定なＡｇＯをア
ルコールにより還元して安定化させるものである。The present invention mainly involves stabilizing unstable AgO in which X is 1.0 or more by reducing it with alcohol.
以下本発明をその実施例により説明する。The present invention will be explained below with reference to Examples.
まず、ＮａＯＨを７２１／ｌの割合で溶解した温度８５
℃のＮａＯＨ水溶液に硝酸銀及び酸化剤の過硫酸カリウ
ムをそれぞれ５１ｙ／ｌ及び７５９／ｌの割合で加えて
ＡｇＯを生成させる。First, the temperature at which NaOH was dissolved at a rate of 721/l was 85
AgO is produced by adding silver nitrate and potassium persulfate as an oxidizing agent to a NaOH aqueous solution at a temperature of 51 y/l and 759/l, respectively.
このＡｇ０を室温において各種アルコールに約１時間浸
漬し、水洗乾燥の後、温度７０℃の４０重量％ＫＯＨ水
溶液中に４時間浸漬した場合のＡｇ０の分解により生成
する酸素ガス量から求めた平均ガス発生速度を第１表に
示す。なお同表には各種アルコールで処理したＡｇＯを
５００℃の温度で１時間加熱して熱分解させた場合の重
量減から求めたＡｇＯｘにおけるｘ値も示す。以上の結
果から明らかなようにアルコールで処理したＡｇＯはＡ
ｇＯｘで表した場合のＸ値が減少し分解によるガス発生
速度が著しく抑制されることがわかる。This Ag0 was immersed in various alcohols at room temperature for about 1 hour, washed with water, dried, and then immersed in a 40% KOH aqueous solution at a temperature of 70°C for 4 hours.The average gas was determined from the amount of oxygen gas generated by the decomposition of Ag0. The generation rate is shown in Table 1. The same table also shows the x value of AgOx determined from the weight loss when AgO treated with various alcohols was thermally decomposed by heating at a temperature of 500° C. for 1 hour. As is clear from the above results, AgO treated with alcohol is A
It can be seen that the X value expressed in gOx decreases and the rate of gas generation due to decomposition is significantly suppressed.
なおメチルアルコール及びエチルアルコールを用いた場
合には、その還元作用が強いため、ＡｇＯをＡ，２Ｏあ
るいはＡ８にまで還元するためＡ８Ｑ舌物質として利用
できない。Note that when methyl alcohol and ethyl alcohol are used, their reducing action is strong and AgO is reduced to A, 2O, or even A8, so that it cannot be used as an A8Q tongue substance.
又これらアル］−ルによる処理時間を短くすると安定な
ＡｇＯまで分解するのでガス発生が多くなる。上例では
アルコールへの浸漬時間を１時間としたが、約５時間程
度としても効果は変わらない。Furthermore, if the treatment time with these alcohols is shortened, stable AgO is decomposed, resulting in increased gas generation. In the above example, the immersion time in alcohol was set to 1 hour, but the effect remains the same even if it is about 5 hours.
次に室温において各種アルコールで１時間処理したＡｇ
Ｏに２重量％の弗素樹脂を加えて圧縮成型した正極、１
０重量％アマルガム化した亜鉛を活物質とする負極、４
０重量％のＫＯＨ水溶液に酸化亜鉛を飽和させた電解液
を用いて、直径１１６ｍｍ１高さ４．２ｍｍの電池を構
成し、６０℃の温度で１力月間放置した場合の電池の高
さ方向の膨張度合を比較すると、第２表の如くであつた
。以上の結果から明らかなように、本発明の正極を用い
れは、ＡｇＯの分解によるガス発生を抑制し、電池の膨
張度も極めて小さくなるので、実用的な密閉式酸化銀電
池を構成することができる。Ag was then treated with various alcohols for 1 hour at room temperature.
Positive electrode made by adding 2% by weight of fluororesin to O and compression molding, 1
Negative electrode containing 0% by weight amalgamated zinc as active material, 4
A battery with a diameter of 116 mm and a height of 4.2 mm is constructed using an electrolyte containing 0% by weight KOH aqueous solution saturated with zinc oxide. A comparison of the degrees of expansion was as shown in Table 2. As is clear from the above results, when the positive electrode of the present invention is used, gas generation due to decomposition of AgO is suppressed and the degree of expansion of the battery is extremely small, so that it is not possible to construct a practical sealed silver oxide battery. can.
Claims (1)
化銀を、一般式Ｃ＿ｎＨ＿２＿ｎ＿＋＿１ＯＨ（ただし
ｎ＝３〜１０）で表されるアルコールで還元して前記Ａ
ｇＯ＿ｘのｘ値を０．９〜１．０とする工程を有するこ
とを特徴とする酸化銀電池用正極の製造法。1 AgO_x (where x>1.0) is reduced with an alcohol represented by the general formula C_nH_2_n_+_1OH (where n = 3 to 10) to obtain the above A.
A method for producing a positive electrode for a silver oxide battery, comprising a step of adjusting the x value of gO_x to 0.9 to 1.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12576276A JPS5924494B2 (en) | 1976-10-19 | 1976-10-19 | Manufacturing method of positive electrode for silver oxide batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12576276A JPS5924494B2 (en) | 1976-10-19 | 1976-10-19 | Manufacturing method of positive electrode for silver oxide batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5350447A JPS5350447A (en) | 1978-05-08 |
| JPS5924494B2 true JPS5924494B2 (en) | 1984-06-09 |
Family
ID=14918182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12576276A Expired JPS5924494B2 (en) | 1976-10-19 | 1976-10-19 | Manufacturing method of positive electrode for silver oxide batteries |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5924494B2 (en) |
-
1976
- 1976-10-19 JP JP12576276A patent/JPS5924494B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5350447A (en) | 1978-05-08 |
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