JPS5999662A - Production method of silver (ii) oxide cell - Google Patents

Abstract

PURPOSE:To reduce the internal resistance and improve the closed-circuit voltage by mixing an active material using silver (II) oxide as a main component then adding a grease-like binder to form a molded positive electrode black mix, and storing it in a cell. CONSTITUTION:5pts.wt. of lead dioxide is added to an active material made of 50pts.wt. each of silver (II) oxide and silver ( I ) oxide, and 1pts.wt. of fluorogrease is added to it and mixed. It is pressurized and molded at a pressure of 5t/cm<2> to form a molded positive electrode black mix 1. This black mix 1 is inserted into a positive electrode can 2 injected with part of an alkaline electrolyte, and a separator 3 and an electrolyte absorber 4 are mounted in sequence. Next, an annular gasket 7 is inserted in the peripheral section and is coupled with a negative electrode terminal plate 5 filled with a negative electrode 6 using amalgamated zinc as an active material and most of the remaining alkaline electrolyte, and the opening section of the positive electrode can 2 is tightened and bent inward so that its inner periphery is brought into contact by pressure with the annular gasket 7 for sealing.

Description

【発明の詳細な説明】 この発明は酸化第二銀（Ａｇｅ）を陽極主活物質従来の
この種電池は、酸化第二銀またはこれと酸化第一銀との
混合物からなる陽極活物質に導電助剖としての二酸化鉛
と離型性や強度向上のためのフッ素グリースの如きバイ
ンダとを同時に添加混合したのち、加圧成形して成形陽
極合剤をつくり、これを電池内に収納する方法でつくら
れているが、この場合電池の内部抵抗が高くかっばらつ
いて電池の閉路電圧か低かったり安定した閉路電圧が得
られなくなる懐みがあった。DETAILED DESCRIPTION OF THE INVENTION This invention uses silver oxide (Age) as the main active material for the anode. In this method, lead dioxide as an anode and a binder such as fluorine grease to improve mold releasability and strength are added and mixed at the same time, and then pressure molded to create a molded anode mixture, which is then stored inside the battery. However, in this case, the internal resistance of the battery is high and unstable, resulting in a low battery closing voltage or an inability to obtain a stable closing voltage.

この発明者らは、上記原因につき詳細に調べた結果、離
型性や強度向上のために用いている前記のグリース状バ
インダが電池の内部抵抗ないし閉路電圧に悪影響を与え
ていることに気付いた。すなわち、フッ素グリースの如
きグリース状のバインダは二酸化鉛に対するよりも陽極
活物質に対してその親和性が強く、合剤成形に当たって
上記王者を同時混合したときは、陽極活物質の表面にフ
ッ素グリースなどが優先的に付着し、この付着膜が上記
活物質と二酸化鉛との接触を妨は二酸化鉛の導電機能を
損なう結果となる。As a result of a detailed investigation into the above-mentioned causes, the inventors realized that the aforementioned grease-like binder, which is used to improve mold releasability and strength, had an adverse effect on the internal resistance or closed-circuit voltage of the battery. . In other words, a grease-like binder such as fluorine grease has a stronger affinity for the anode active material than it does for lead dioxide, and when the above-mentioned kings are simultaneously mixed during mixture forming, fluorine grease etc. preferentially adheres, and this adhered film prevents contact between the active material and lead dioxide, resulting in damage to the conductive function of lead dioxide.

この発明は、上記の知見をもとにしてさらに検討した結
果見い出されたものであり、その要旨とするところは酸
化第二銀を主成分とする活物質と導電助剤としての二酸
化鉛とを混合したのち、グリース状のバインダを加えて
加圧成形することにより成形陽極合剤をつくり、これを
電池内に収納することを特徴とする酸化第二銀電池の製
造法にある。This invention was discovered as a result of further study based on the above knowledge, and its gist is that an active material containing silver oxide as a main component and lead dioxide as a conductive aid are used. After mixing, a grease-like binder is added and pressure molded to produce a molded anode mixture, which is then housed in a battery.

すなわち、上記方法によれば、活物質と二酸化鉛とをよ
くなじませた状態でバインダを添加混合するものである
ため、従来の如き活物質と二酸化鉛との極端な接触妨害
が阻止されて、そのぶん電池の内部抵抗を低下させ閉路
電圧を向上することが可能となる。That is, according to the above method, since the binder is added and mixed with the active material and lead dioxide in a well-mixed state, the extreme interference with contact between the active material and lead dioxide as in the conventional method is prevented. Accordingly, it is possible to reduce the internal resistance of the battery and improve the closed circuit voltage.

この発明に適用される活物質は酸化第二銅単独であって
もよいしこれと酸化第−銀との混合物であってもよい。The active material applied to this invention may be cupric oxide alone or a mixture of cupric oxide and silver oxide.

また、上記酸化第二銀を部分還元してその表面層に酸化
第−銀を形成したものであっても差し支えない。これに
混合する二酸化鉛の添加量としては活物質１００重量部
に対して通常３〜１０重量部程度である。Further, it is also possible to partially reduce the above-mentioned silver oxide to form silver oxide on the surface layer. The amount of lead dioxide to be added to this is usually about 3 to 10 parts by weight per 100 parts by weight of the active material.

上記活物質と二酸化鉛とをよく混合したのち、これにグ
リース状のがインタを添加混合するが、このバインダの
代表的なものは、すでに述べたフッ素グリース、つまり
低分子量のポリトリフルオルクロルエチレンに高分子量
固形のポリテトラフルオルエチレンを分散混合してなる
ものである。After thoroughly mixing the above active material and lead dioxide, a grease-like binder is added and mixed.A typical example of this binder is the already mentioned fluorine grease, that is, low molecular weight polytrifluorochloroethylene. It is made by dispersing and mixing high molecular weight solid polytetrafluoroethylene.

この種ハインタの添加量は活物質１００重量部に対して
通常０．５〜３重量部である。The amount of this type of hindrance added is usually 0.5 to 3 parts by weight per 100 parts by weight of the active material.

バインダを添加混合したのちは常法により加圧成形して
成形陽極合剤となし、これを電池内に収納することによ
り、この発明の目的とする高くてかつ安定した閉路電圧
を有する酸化第二銀電池を得ることかできる。After adding and mixing the binder, the mixture is press-molded using a conventional method to form a molded anode mixture, and this is stored in a battery to produce a secondary oxide having a high and stable closed circuit voltage, which is the object of the present invention. Can you get silver batteries?

以下に、この発明の実施例を記載してより具体的に説明
する。EXAMPLES Below, examples of the present invention will be described in more detail.

実施例 酸化第二銀５０重量部と酸化第−銀５０重量部とからな
る活物質に対し５重量部の二酸化鉛を加え、乳鉢でよく
混合した。これにフッ素グリース１重量部を加え再びよ
く混合した。これを２６０〜取り、５トン／　ｃＪの圧
力で加圧成形して、直径９闘、厚み０．７朋の成形陽極
合剤をつくった。この合剤を用いて常法により図示され
る如きボタン型の酸化第二銀電池を作製した。Example 5 parts by weight of lead dioxide were added to an active material consisting of 50 parts by weight of ferric oxide and 50 parts by weight of silver oxide, and the mixture was thoroughly mixed in a mortar. 1 part by weight of fluorine grease was added to this and mixed well again. This was taken from 260 mm and press-molded at a pressure of 5 tons/cJ to produce a molded anode mixture with a diameter of 9 mm and a thickness of 0.7 mm. Using this mixture, a button-shaped ferric oxide battery as shown in the figure was prepared by a conventional method.

すなわち、アルカリ電解液の一部が注入された陽極缶２
に前記の成形陽極合剤１を挿入し、この合剤１上にセパ
レータ３および電解液吸収体４を順次載置した。That is, the anode can 2 into which a part of alkaline electrolyte is injected
The above-mentioned molded anode mixture 1 was inserted, and the separator 3 and electrolyte absorber 4 were placed on this mixture 1 in this order.

つきに、この状態の陽極缶２を、周縁部に環状ガスケッ
ト７を嵌着させかつ７５〜のアマルガム化亜鉛を活物質
とする陰極６と残り大半部のアルカリ電解液とを内填し
た陰極端子板５に嵌合し、陽極缶２の開口部を内方へ締
め付けわん曲させてその内周面を環状ガスケット７に圧
接させて封口することにより、図に示すような構成のボ
タン型の酸化第二銀電池を作製した。At the same time, the anode can 2 in this state is fitted with an annular gasket 7 around its periphery, and a cathode terminal containing a cathode 6 containing amalgamated zinc as an active material from 75 to 75 and an alkaline electrolyte containing the remaining majority. A button-shaped oxidizer having the configuration shown in the figure is formed by fitting the plate 5, tightening and bending the opening of the anode can 2 inward, and pressing the inner peripheral surface against the annular gasket 7 for sealing. A ferric silver battery was produced.

なお、使用した陽極缶２は鉄製で表面をニッケルメッキ
したものであり、陰極端子板５は銅−ステンレス鋼−ニ
ッケルクラッド板製である。セパレータ３としてはセロ
ファンの両側にグラフトフィルム（架橋低密度ポリエチ
レンフィルムにメタクリル酸をグラフト重合させたグラ
フトフィルム）をラミネートした複合膜が使用され、電
解液吸収体４はポリプロピレン不織布からなるものであ
る。アルカリ電解液としては酸化亜鉛を溶解させた２５
重量％の苛性ソーダ水溶液を使用した。また、電池（ボ
タン型）の直径は９．５　ｍｒｎ、高さは２．７　ｍｍ
である。The anode can 2 used was made of iron and had its surface plated with nickel, and the cathode terminal plate 5 was made of a copper-stainless steel-nickel clad plate. As the separator 3, a composite membrane is used in which a graft film (a graft film obtained by graft polymerizing methacrylic acid to a crosslinked low-density polyethylene film) is laminated on both sides of cellophane, and the electrolyte absorber 4 is made of a polypropylene nonwoven fabric. As an alkaline electrolyte, 25 in which zinc oxide is dissolved is used.
A % by weight aqueous solution of caustic soda was used. Also, the diameter of the battery (button type) is 9.5 mrn, and the height is 2.7 mm.
It is.

この酸化第二銀電池につき、２にΩ５秒負荷後の閉路電
圧を調べた結果は、下記の表に示されるとおりであった
。なお、表中の比較例とは、活物質と二酸化鉛とフッ素
グリースとを同時に添加混合する方式を採った以外は実
施例と同様にして作製した従来の酸化第二銀電池の上記
同様の試験結果を示したものである。The closed circuit voltage of this silver oxide battery after being loaded with 2 Ω for 5 seconds was investigated, and the results were as shown in the table below. The comparative example in the table is a test similar to the above of a conventional silver oxide battery manufactured in the same manner as the example except that the active material, lead dioxide, and fluorine grease were added and mixed at the same time. The results are shown below.

上記の結果から明らかなように、この発明法によれは閉
路電圧が高くてかつ安定した酸化第二銀電池が得られる
ものであることがわかる。As is clear from the above results, it can be seen that according to the method of the present invention, a stable silver oxide battery with a high closed circuit voltage can be obtained.

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

図面はこの発明法によって得た酸化第二銀電池の一例を
示す断面図である。 １・・・成形陽極合剤。The drawing is a sectional view showing an example of a silver oxide battery obtained by the method of this invention. 1... Molded anode mixture.

Claims (1)

【特許請求の範囲】[Claims] （１）酸化第二銀を主成分とする活物質と導電助剤とし
ての二酸化鉛とを混合したのち、グリース状のバインダ
を加えて加圧成形することにより成形陽極合剤をつくり
、これを電池内に収納することを特徴とする酸化第二銀
電池の製造法。(1) After mixing an active material mainly composed of silver oxide and lead dioxide as a conductive agent, a grease-like binder is added and pressure molded to create a molded anode mixture. A method for manufacturing a ferric oxide battery, characterized in that the battery is housed within a battery.