JPS62140367A - Silver oxide cell - Google Patents

Abstract

PURPOSE:To stabilize the inner resistance of a cell, by preparing a flake form silver powder including a specific ratio of a high grade fatty acid as an electroconductivity asisting agent, and mixing the agent to silver oxide powder to make a positive electrode. CONSTITUTION:To silver oxide which is a main active substance, a flake form silver powder containing 0.2-2.0wt% of a high grade fatty acid is mixed and compressed to form composite pellets 1. The composite pellets 1 are inserted in a positive electrode case 2 and, together with a positive ring 3, compressed to form the positive electrode side. In such a composition, the mixing of the silver powder with the silver oxide can be made even to make even the conductivity inside the silver oxide powder. Therefore, the inner resistance of the cell is stabilized and a satisfactory low temperature discharge property can be realized.

Description

【発明の詳細な説明】 産業上の利用分野 本発明ｄ：、酸化銀を主剤とした正極を用いる酸化銀電
池に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention d: relates to a silver oxide battery using a positive electrode mainly composed of silver oxide.

従来の技術 従来酸化銀を主剤とする正極活物質を用いたボタン形酸
化銀電池は、負極に亜鉛を用いた電池が商品化されてい
る。この電池は、正極として酸化銀粉末に５重量％の黒
鉛粉末を混合して圧縮成形したものが用いられている。BACKGROUND OF THE INVENTION Conventionally, button-shaped silver oxide batteries using a positive electrode active material containing silver oxide as a main ingredient have been commercialized, and batteries using zinc as a negative electrode have been commercialized. This battery uses, as a positive electrode, a mixture of silver oxide powder and 5% by weight of graphite powder, which is compression-molded.

近年、このボタン形酸化銀電池は、これを電源とする使
用機器、例えば電子腕時計、電卓等の小形、薄形化に伴
い、高電気容量化が要望されている。In recent years, there has been a demand for button-shaped silver oxide batteries with higher electrical capacity as devices that use them as power sources, such as electronic wristwatches and calculators, have become smaller and thinner.

２ページ この高電気容量化として正極体の電導助剤である黒鉛に
比べて嵩密度の高い銀粉末を用いることが提案されてい
る。この方法は、酸化銀粉末にフレーク状の銀粉末を５
重量％混合し、圧縮成形したものである。この方法を採
れば、黒鉛を混合したＩＦ極体に比べ、約１・２倍の高
電気容量化が図れる。Page 2 To increase the electric capacity, it has been proposed to use silver powder, which has a higher bulk density than graphite, which is a conductive agent in the positive electrode body. This method involves adding 50% of flaky silver powder to silver oxide powder.
They were mixed in weight percent and compression molded. If this method is adopted, the electric capacity can be increased by about 1.2 times compared to an IF pole body containing graphite.

発明が解決しようとする問題点 しかし、フレーク状の銀粉末を混合する場合、フレーク
状の銀粉末相互がからみ合って２次粒子を取り易く、酸
化銀粉末と混合した場合、均一に混合できない問題点が
ある。この場合には電池に組み立てた時の電池内部抵抗
のバラツキが生じ、低温放電特性が満足できない電池が
ある。本発明はこのような問題点を解決することを目的
としたものである。Problems to be Solved by the Invention However, when mixing flaky silver powder, the flaky silver powder becomes entangled with each other, making it easy to remove secondary particles, and when mixing with silver oxide powder, there is a problem that uniform mixing is not possible. There is a point. In this case, variations occur in the internal resistance of the battery when it is assembled into a battery, and some batteries may not have satisfactory low-temperature discharge characteristics. The present invention aims to solve these problems.

問題点を解決するだめの手段 この問題点を解決するため本発明は、高級脂肪酸を０．
２〜２．０重量％を含んだフレーク状の銀粉末を電導助
剤とし、これを酸化銀粉末と混合して３　へ− 圧縮成形し、正（愼とし／こものである。Alternative Means to Solve the Problem In order to solve this problem, the present invention provides higher fatty acids with 0.
Flake-like silver powder containing 2 to 2.0% by weight is used as a conductive additive, mixed with silver oxide powder, and compression molded into 3.

作用 この構成によれば、酸化４１Ｖ！との混合を均一にでき
、酸化銀粉末間の電導性を均一にできる。これは従来の
方法であればフレーク状銀粉末が２次粒子を作シ均−混
合ができないのに対して、この構成であればフレーク状
銀粉末間に２次粒子ができないことから分散しやすく、
均一混合ができるからである。Effect: According to this configuration, the oxidation voltage is 41V! The silver oxide powder can be uniformly mixed with the silver oxide powder, and the conductivity between the silver oxide powders can be made uniform. This is because with the conventional method, flaky silver powder creates secondary particles and cannot be evenly mixed, but with this configuration, secondary particles are not formed between flaky silver powders, making it easier to disperse. ,
This is because uniform mixing can be achieved.

実施例 以下、本発明の詳細な説明する。Example The present invention will be explained in detail below.

酸化銀に、ステアリン酸０１重１ｎ：％含んだ厚みが０
．１μｍ、平均粒径が１／Ａｍのフレーク状銀粉末を５
重量％混合し、２トンの圧力で圧縮成形して合剤ベレッ
ト１を作り、これを正極ケース２に挿入して正極リング
３とともに３トンで圧縮成形して正極側を構成ｉ〜だ。The thickness of silver oxide containing stearic acid 01 weight 1n:% is 0
．． 5 pieces of flaky silver powder with an average particle size of 1 μm and 1/Am
They are mixed in weight percent and compression molded under a pressure of 2 tons to produce a mixture pellet 1, which is inserted into a positive electrode case 2 and compression molded together with a positive electrode ring 3 under a pressure of 3 tons to form the positive electrode side.

次に負極側は、氷化亜鉛粉末にポリアクリル酸ソーダ５
重量％を混合した負極合剤４を負（ナケース６に充填し
、これに水酸化す）　ＩＪウノ、の８モル／ａ水溶液に
酸化叱鉛３重量の溶解させたアルカリ電解液を注液し、
多孔性ポリエチレンフィルムからなるセパレータ６とナ
イロン不織布からなる電解液含浸材７を挿入して構成す
る。８はナイロンからなるシール材である。Next, on the negative electrode side, add 50% sodium polyacrylate to the frozen zinc powder.
An alkaline electrolyte containing 3 weight of lead oxide dissolved in an 8 mol/a aqueous solution of IJ UNO was poured into the negative electrode mixture 4 mixed with % by weight (filled in the nacase 6 and hydroxylated there). ,
It is constructed by inserting a separator 6 made of a porous polyethylene film and an electrolyte impregnated material 7 made of a nylon nonwoven fabric. 8 is a sealing material made of nylon.

図はこのようにして組み立てた酸化銀電池を示す。The figure shows a silver oxide battery assembled in this manner.

このようにして電池サイズが直径６．８だし厚み２πＦ
の電池組立体を電池ａとする。次に、上記のステアリン
酸を０．２重量％、０．６重量％、１．５重量％、２．
０重量％、２．５重量％とし、上記と同様にして相み立
てた電池組立体をそれぞれ電池ｂ１電池Ｃ１電池ｄ１電
池ｅ１電池ｆとする。In this way, the battery size is 6.8 in diameter and 2πF in thickness.
The battery assembly of is designated as battery a. Next, the above stearic acid was added to 0.2% by weight, 0.6% by weight, 1.5% by weight, 2.
0% by weight and 2.5% by weight, and the battery assemblies assembled in the same manner as above are designated as battery b1 battery C1 battery d1 battery e1 battery f.

また従来例として、酸化銀に厚みが０．１μｍ、平均粒
子径が１μｍのフレーク状銀粉末を５重量％混合し、以
下上記と同様にして組み立てた電池組立体をｇとする。Further, as a conventional example, a battery assembly prepared by mixing silver oxide with 5% by weight of flaky silver powder having a thickness of 0.1 μm and an average particle diameter of 1 μm and assembled in the same manner as described above is referred to as g.

とれらの電池を各５ｏ個組み立てた。この時の電池内部
抵抗を第１表に示す。I assembled 50 of each of these batteries. Table 1 shows the battery internal resistance at this time.

Ｃ以下余　白） ５ベーノ 第１表 次に上記電池ａ　−ｇを時開の実用試験である低温放電
試験を行なった。なお試験方法は、−１０°Ｃで２にΩ
、５秒間放電時の最低維持重圧を測定した。この結果を
第２表に示す。5 Beno Table 1 Next, the above batteries a to g were subjected to a low-temperature discharge test, which is a practical test of time opening. The test method is 2Ω at -10°C.
The minimum sustained pressure during discharge for 5 seconds was measured. The results are shown in Table 2.

（以下余　白） ６ページ 第２表 この結果よυ従来のフレーク状銀粉末のみを混合した電
池ｇ１およびステアリン酸０．１重量％含んだフレーク
状銀粉末を混合した電池ａ１ステアリン酸２．５重量％
含んだフレーク状銀粉末を混合した電池ｆは、電池内部
抵抗のバラツキが大きく、時計の実用試験であるステッ
プモータの駆動電圧が維持できないっこのステップモー
タの駆動電圧に必要な維持電圧は１・１ｏｖといわれて
いる。また、本発明によるステアリン酸０・２〜２・○
重量％７ベ 含んだフレーク状銀粉末を用いた電池ｂ　−ｅは、低温
でもステップモータの駆動が可能である。これは、従来
法のフレーク状４ＪＶ！粉末を混合した場合、およびス
テアリン酸０．１重］１；゛％含んだフレ・−り状銀粉
末を混合した場合、フレーク状銀粉末が２次粒子を作り
酸化銀粉末間に均一に混ざらないために電気伝導性のバ
ラツキを生じ、電池内部抵抗のバラツキを生じる。また
、ステアリン酸２．５重量％含んだフレーク状銀粉末を
混合した場合は、酸化銀粉末間に均一に混ざるが、高伝
導性のフレーク状銀粉末を高抵抗のステアリン酸で包み
こむ状態になる。したがって酸化銀粉末間の伝導性が保
たれなくなり電池内部抵抗のバラツキとなる。(Leaving space below) Table 2 on page 6 The results are υBattery g1 mixed with only conventional flaky silver powder and battery a1 mixed with flaky silver powder containing 0.1% by weight of stearic acid2.5% stearic acid weight%
Battery f, which contains flaky silver powder, has large variations in battery internal resistance, and cannot maintain the driving voltage of the step motor used in the practical test of watches.The required maintenance voltage for the step motor driving voltage is 1. It is said to be 1ov. In addition, stearic acid 0.2 to 2.○ according to the present invention
Batteries b to e using flaky silver powder containing 7% by weight can drive step motors even at low temperatures. This is the flaky 4JV of the conventional method! When powders are mixed, and when flaky silver powder containing 0.1% stearic acid is mixed, the flaky silver powder forms secondary particles and is not uniformly mixed between the silver oxide powders. This causes variations in electrical conductivity and variations in battery internal resistance. Furthermore, when flaky silver powder containing 2.5% by weight of stearic acid is mixed, it is mixed uniformly between the silver oxide powders, but the highly conductive flaky silver powder is surrounded by the highly resistive stearic acid. Become. Therefore, conductivity between the silver oxide powders is not maintained, resulting in variations in battery internal resistance.

しかし、本発明のステアリン酸０．２〜２．０重量％を
含んだフレーク状銀粉末は２次粒子を作らず、酸化銀粉
末間に均一に混合することができ、高抵抗がステアリン
酸の影響を受け々いことから電気伝導性が安定して得ら
れる。寸だ、ここではステアリン酸を用いたものを例に
挙げたが、オレイン酸についても同様のことが言える。However, the flaky silver powder containing 0.2 to 2.0% by weight of stearic acid of the present invention does not form secondary particles and can be uniformly mixed between silver oxide powders, and the high resistance is that of stearic acid. Since it is not easily affected, stable electrical conductivity can be obtained. Although I used stearic acid as an example, the same can be said for oleic acid.

したがって高級脂肪酸であれば、同様の結果が得られる
。Therefore, similar results can be obtained with higher fatty acids.

発明の効果 以上のように本発明によれば、電導助剤に高級脂肪酸０
．２〜２，０重量％含んだフレーク状銀粉末を用いるこ
とにより、電池の内部抵抗が安定し、低温放電特性を満
足することができ、時計用電源として好適な酸化銀電池
が得られる。Effects of the Invention As described above, according to the present invention, the conduction aid contains 0 higher fatty acids.
．． By using flaky silver powder containing 2 to 2.0% by weight, the internal resistance of the battery is stabilized, low-temperature discharge characteristics can be satisfied, and a silver oxide battery suitable as a power source for watches can be obtained.

【図面の簡単な説明】[Brief explanation of drawings]

図は本発明の実施例における電池の断面図を示す。 ２・・・正極ペレット、２・・・・正極ケース、３・°
。 ・・正極リング、４・・・・・負極合剤、５　・・・負
極ケース、６・・−・・・セパレータ、７・・・電解液
含浸材、８・−・・・シール材。The figure shows a cross-sectional view of a battery in an embodiment of the invention. 2...Positive electrode pellet, 2...Positive electrode case, 3.°
. ...Positive electrode ring, 4...Negative electrode mixture, 5...Negative electrode case, 6...Separator, 7...Electrolyte impregnation material, 8...Sealing material.

Claims (1)

【特許請求の範囲】[Claims] 主活物質である酸化銀に、高級脂肪酸を０．２〜２．０
重量％含んだフレーク状銀粉末を混合した正極を備えた
ことを特徴とする酸化銀電池。Silver oxide, the main active material, contains 0.2 to 2.0 higher fatty acids.
1. A silver oxide battery comprising a positive electrode mixed with flaky silver powder containing % by weight.