JPH0212762A - Silver oxide battery - Google Patents
Silver oxide batteryInfo
- Publication number
- JPH0212762A JPH0212762A JP16331288A JP16331288A JPH0212762A JP H0212762 A JPH0212762 A JP H0212762A JP 16331288 A JP16331288 A JP 16331288A JP 16331288 A JP16331288 A JP 16331288A JP H0212762 A JPH0212762 A JP H0212762A
- Authority
- JP
- Japan
- Prior art keywords
- positive electrode
- silver oxide
- carbon
- manganese dioxide
- silver
- 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
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910001923 silver oxide Inorganic materials 0.000 title claims abstract description 24
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 229910052709 silver Inorganic materials 0.000 claims abstract description 7
- 239000004332 silver Substances 0.000 claims abstract description 7
- 239000011149 active material Substances 0.000 claims abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000000748 compression moulding Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000009467 reduction Effects 0.000 abstract 1
- 238000007789 sealing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000035936 sexual power Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 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
- H01M4/02—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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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
- H01M6/12—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with flat electrodes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (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 本発明は、酸化銀電池の改良に関するものである。[Detailed description of the invention] Industrial applications The present invention relates to improvements in silver oxide batteries.
従来の技術
酸化銀”１池は、時計用などの電子機器の電源として広
く利用されているが、特にＩＣ，ＬＳＩの集積回路技術
の進歩により、消費電流の低下からその機器・電源の長
期信頼性の向上が求められている。Conventional technologySilver oxide batteries are widely used as power sources for electronic devices such as watches, but advances in IC and LSI integrated circuit technology in particular have led to lower current consumption and improved long-term reliability of devices and power sources. There is a need for improvement in sexual performance.
又小形、薄形化に伴い高電気容量化が要望されている。In addition, as devices become smaller and thinner, higher electrical capacity is desired.
長期信頼性よりみると、一般に酸化銀電池は、酸化銀の
アルカリ電解液への溶解反応により、電気容量が低下し
、又、酸化第−銀の場合Ａｃｒ（○Ｈ）２−となって溶
解し、これが負極側へ拡散し、セパレータや亜鉛を酸化
させ電池を劣化させる。In terms of long-term reliability, silver oxide batteries generally have a reduced electrical capacity due to the dissolution reaction of silver oxide in an alkaline electrolyte, and in the case of silver oxide, it becomes Acr(○H)2- and dissolves. However, this diffuses to the negative electrode side, oxidizes the separator and zinc, and deteriorates the battery.
又、酸化銀と接触するセパレータは、酸化銀の強い酸化
力により酸化分解され、長期保存性のうえで、大きな問
題となる。Furthermore, the separator that comes into contact with silver oxide is oxidized and decomposed due to the strong oxidizing power of silver oxide, which poses a major problem in terms of long-term storage.
従来この問題全改善する方法として耐酸化性のより強い
セパレータなどの材料を使用する方法もあるが、保存特
性、閉路電圧特性などの充分な確認が必要であり実際的
な改善方法ではない。高７Ｅ気容量化としては、正極体
の電導助剤として、嵩密度の低いリン状黒鉛あるいは人
造黒鉛を用いるのに代えて以下の様な提案がなされてい
る。すなわち顆粒酸化銀を還元して粒子の表面に金属銀
層を形成したものを加圧成型して正極物質として構成す
ることによって、その金属銀層のネットワークを利用し
て電導性を保つ方法でろる。あるいは、金属銀粉末を酸
化銀粉末に添加させ、電導性全保ち正甑物質とする。Conventionally, there is a method to completely overcome this problem by using a material such as a separator with stronger oxidation resistance, but this is not a practical method of improvement as it requires thorough confirmation of storage characteristics, closed circuit voltage characteristics, etc. In order to achieve a high 7E air capacity, the following proposals have been made in place of using phosphorous graphite or artificial graphite, which have a low bulk density, as a conductive additive in the positive electrode body. In other words, by reducing granular silver oxide to form a metallic silver layer on the surface of the particles and forming the positive electrode material by pressure molding, the network of the metallic silver layer is used to maintain conductivity. . Alternatively, metallic silver powder is added to silver oxide powder to form a solid material that maintains full electrical conductivity.
これらの方法を採れば、黒鉛全混合した正極体に比べ、
約１．１倍の高電気容量化が図れる。If these methods are adopted, compared to a positive electrode body made entirely of graphite,
The electric capacity can be increased by about 1.1 times.
発明が解決しようとする課題
このような従来の方法においては、以下の２つの問題が
あった。Problems to be Solved by the Invention This conventional method has the following two problems.
（１）正極合剤表面とセパレータが接触しているため、
セパレータの酸化分解により、電解液に溶解した酸化銀
の負極側への拡散が容易になり保存性に問題があった。(1) Because the positive electrode mixture surface and separator are in contact,
Due to oxidative decomposition of the separator, silver oxide dissolved in the electrolytic solution easily diffuses to the negative electrode side, causing a problem in storage stability.
（２） 高電気容量化は図れたが、放電末期の閉路電
圧特性の低下が大きいという問題があった。(2) Although a high electric capacity was achieved, there was a problem in that the closed circuit voltage characteristics at the end of discharge were significantly reduced.
本発明は、上記の様な問題点を解消し、高電気容量の成
極体を用いて、保存性能、閉路”７Ｅ圧特性にすぐれた
酸化銀電池を提供することを目的とする。An object of the present invention is to solve the above-mentioned problems and provide a silver oxide battery that uses a polarized body of high electric capacity and has excellent storage performance and closed circuit "7E pressure characteristics."
課題を解決するための手段
上記の問題全解決するため本発明は酸化銀を活物質とし
、金属銀１［導助剤とした正極合剤の負甑対向面側及び
正極ケースに接する面側の両方に、二酸化マンガンとカ
ーボンと混合層を形成したものである。Means for Solving the Problems In order to solve all of the above problems, the present invention uses silver oxide as an active material, metal silver 1 [as a conductive agent] of the positive electrode mixture on the side facing the negative electrode and on the side in contact with the positive electrode case. A mixed layer of manganese dioxide and carbon is formed on both.
作 用
この構成によれば、正極合剤の負極の対向面側に、二酸
化マンガンとカーボンを混合した層全形成することによ
り、セパレータへの直接の酸化銀による酸化、混合した
酸化銀の拡散が少なく保存劣化の小さな酸化銀電池を得
ることができる。Effect: According to this configuration, by forming the entire layer of a mixture of manganese dioxide and carbon on the opposite surface of the negative electrode of the positive electrode mixture, direct oxidation of the separator by silver oxide and diffusion of the mixed silver oxide are prevented. A silver oxide battery with less storage deterioration can be obtained.
又、正極合剤の正極ケースに接する面に同様の二酸化マ
ンガンとカーボンを混合した層を形成することにより、
その原理は明確でないが放電末期の閉路電圧特性の向上
に役立つことになる。In addition, by forming a layer of a similar mixture of manganese dioxide and carbon on the surface of the positive electrode mixture that contacts the positive electrode case,
Although the principle is not clear, it is useful for improving the closed circuit voltage characteristics at the end of discharge.
実施例 以下、本発明の実施例を示す。Example Examples of the present invention will be shown below.
第１図は、本発明による直径９．６ｍｍ 、高さ２，０
咽の酸化銀電池５Ｒ９２０Ｗを示す。Figure 1 shows a diameter of 9.6 mm and a height of 2.0 mm according to the present invention.
A silver oxide battery 5R920W is shown.
図中１は正極ケース、２は本発明による正極合剤であり
、顆粒状酸化銀の粒子の表面を還元して金属銀層を形成
した粒子を加圧成型したもの２と負極の対向面側及び反
対の正極ケースに接する面側に二酸化マンガンとカーボ
ンを混合した層９よりなり、正極ケース１内に正極リン
グ３とともに挿入して圧縮成型をする。In the figure, 1 is a positive electrode case, and 2 is a positive electrode mixture according to the present invention, which is obtained by pressure molding particles in which the surface of granular silver oxide particles is reduced to form a metallic silver layer.2 and the opposite side of the negative electrode. and a layer 9 made of a mixture of manganese dioxide and carbon on the side that contacts the opposite positive electrode case, and is inserted into the positive electrode case 1 together with the positive electrode ring 3 and compression molded.
そして加圧成型した正極に水酸化カリウム電解液全注液
した後、ポリエチレンからなる微孔性フィルムとセロフ
ァンからなるセパレータ４と、ナイｏン不織布あるいは
セルロースやコツトン等力らなる含浸材５を打ち抜いて
正極ケース１内に挿入した。さらに、その上に水化亜鉛
粉末とゲル化剤としてポリアクリル酸よりなるゲル状亜
鉛負極了を封口板８に保持させて配置し、封口リング６
を介して正極ケースの周縁を締つけることで構成した。After pouring all of the potassium hydroxide electrolyte into the pressure-molded positive electrode, a separator 4 made of a microporous film made of polyethylene and cellophane, and an impregnated material 5 made of nonwoven fabric, cellulose, cotton, etc. are punched out. and inserted it into the positive electrode case 1. Further, a gelled zinc negative electrode made of zinc hydrate powder and polyacrylic acid as a gelling agent is placed on top of the sealing plate 8 and held by the sealing ring 6.
It was constructed by tightening the periphery of the positive electrode case through the
上記の正極合剤の負極の対向面側及び反対の正極ケース
に接する面側に形成した二酸化マンガンとカーボンを混
合し形成した層はＭｎＯ２：Ｃを９０ ： １０の配合
比で用いた。The layer formed by mixing manganese dioxide and carbon on the side facing the negative electrode and the side in contact with the opposite positive electrode case of the positive electrode mixture used MnO2:C in a mixing ratio of 90:10.
この電池ｉＡとする。以下比較例として、Ｂ〜Ｑを第１
表の様に示す。Let this battery be iA. Below, as a comparative example, B to Q are
It is shown in the table.
第１表の条件で製造した電池Ａ−Ｑの初期放電特性、６
０°Ｃ６０日保存後の放電容量残存率、初度内部抵抗、
放νに深度別間路ｆｌｊ圧特性を第２表に示す。Initial discharge characteristics of batteries A-Q manufactured under the conditions shown in Table 1, 6
Discharge capacity residual rate after 60 days storage at 0°C, initial internal resistance,
Table 2 shows the path flj pressure characteristics at different depths.
第２表に示した各項目の測定条件は次の通りである。The measurement conditions for each item shown in Table 2 are as follows.
閉路°電圧・・・・・・温度−１ｏ″Ｃ２負荷抵抗２０
０Ω７−５ＳｅＣ間の最低電圧を各放電深度別に測定
各ｎ ＝ ２０の値
放電容量・・・・・・２Ｑ″Ｃにおける１６にΩ定抵抗
放電で終了°電圧１．４ｖまでａ１悦派を示す
各ｎ ＝ ２０の値
内部抵抗・・・・・・２０°Ｃにおける内部抵抗各ｎ＝
＝１０００値
第
表
第
表
以上の結果よシ負唖側の面に、二酸化マンガン。Closed circuit ° Voltage...Temperature -1o''C2 Load resistance 20
Measure the lowest voltage between 0Ω7-5SeC for each depth of discharge. Value for each n = 20. Discharge capacity... End with a constant resistance discharge of 16Ω at 2Q''C. Shows A1 pleasure up to a voltage of 1.4V. Value of each n = 20 Internal resistance・・・Internal resistance at 20°C Each n =
= 1000 Values Table 1. Manganese dioxide on the negative side.
カーボン、二酸化マンガンとカーボンの層を形成したも
のは、６０°Ｃ保存後の放電容量の残存率は高い。Those in which a layer of carbon, manganese dioxide, and carbon are formed have a high residual discharge capacity after storage at 60°C.
又、カーボンのみの層全形成する電池の放電容量は短い
。In addition, the discharge capacity of a battery in which the entire layer is formed only of carbon is short.
上下両層にカーボンを含む正極合剤は、内部抵抗が低く
初度０％の閉路電圧特性がよい。A positive electrode mixture containing carbon in both the upper and lower layers has low internal resistance and good closed circuit voltage characteristics at 0% initially.
正極ケース側に二酸化マンガンの層を形成する電池は、
８０％深度の閉路電圧の低下がない。Batteries that form a layer of manganese dioxide on the positive electrode case side are
There is no drop in closed circuit voltage at 80% depth.
発明の効果
以上のように、本発明によれば、保存信頼性に優れ安定
した閉路電圧が得られ、放電容量も充分である。Effects of the Invention As described above, according to the present invention, a stable closed-circuit voltage with excellent storage reliability can be obtained, and the discharge capacity is also sufficient.
第１図は本発明の実施例における酸化銀電池の断面図で
ある。
１・・・・・・正極ケース、２・・・・・・正極合剤、
３・・・・・・正極リング、４・・・・・・セパレータ
、５・・・・・・含浸材、６・・・・・・封口リング、
７・・・・・・負極、８・・・・・・封口板、９・・・
・・・二酸化マンガンとカーボンとの混合層。FIG. 1 is a sectional view of a silver oxide battery in an example of the present invention. 1... Positive electrode case, 2... Positive electrode mixture,
3... Positive electrode ring, 4... Separator, 5... Impregnating material, 6... Sealing ring,
7... Negative electrode, 8... Sealing plate, 9...
...Mixed layer of manganese dioxide and carbon.
Claims (1)
の負極対向面側及び正極ケースに接する面側の両方に、
二酸化マンガンとカーボンとを混合形成した酸化銀電池
。Both the side facing the negative electrode and the side in contact with the positive electrode case of the positive electrode mixture using silver oxide as an active material and metallic silver as a conductive aid,
A silver oxide battery made of a mixture of manganese dioxide and carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16331288A JPH0212762A (en) | 1988-06-30 | 1988-06-30 | Silver oxide battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16331288A JPH0212762A (en) | 1988-06-30 | 1988-06-30 | Silver oxide battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0212762A true JPH0212762A (en) | 1990-01-17 |
Family
ID=15771441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16331288A Pending JPH0212762A (en) | 1988-06-30 | 1988-06-30 | Silver oxide battery |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0212762A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5497506A (en) * | 1994-02-18 | 1996-03-05 | Kabushiki Kaisha Kaken Corporation | Portable telephone |
| WO1999027592A1 (en) * | 1997-11-25 | 1999-06-03 | Eveready Battery Company, Inc. | Surface treatment for metal oxide substrates |
| WO2002017414A2 (en) * | 2000-08-24 | 2002-02-28 | The Gillette Company | Battery cathode |
| US7771872B2 (en) | 2003-02-13 | 2010-08-10 | Dowa Electronics Materials Co., Ltd. | Silver oxide powder for alkaline battery and method of producing the same |
| US8721743B2 (en) | 2004-10-21 | 2014-05-13 | The Gillette Company | Battery cathodes |
-
1988
- 1988-06-30 JP JP16331288A patent/JPH0212762A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5497506A (en) * | 1994-02-18 | 1996-03-05 | Kabushiki Kaisha Kaken Corporation | Portable telephone |
| WO1999027592A1 (en) * | 1997-11-25 | 1999-06-03 | Eveready Battery Company, Inc. | Surface treatment for metal oxide substrates |
| US6080283A (en) * | 1997-11-25 | 2000-06-27 | Eveready Battery Company, Inc. | Plasma treatment for metal oxide electrodes |
| WO2002017414A2 (en) * | 2000-08-24 | 2002-02-28 | The Gillette Company | Battery cathode |
| WO2002017414A3 (en) * | 2000-08-24 | 2003-09-25 | Gillette Co | Battery cathode |
| US7045247B1 (en) | 2000-08-24 | 2006-05-16 | The Gillette Company | Battery cathode |
| US7682730B2 (en) | 2000-08-24 | 2010-03-23 | The Gillette Company | Battery cathode |
| US7771872B2 (en) | 2003-02-13 | 2010-08-10 | Dowa Electronics Materials Co., Ltd. | Silver oxide powder for alkaline battery and method of producing the same |
| US8721743B2 (en) | 2004-10-21 | 2014-05-13 | The Gillette Company | Battery cathodes |
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