TW299508B - - Google Patents

Description

A 7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V.-Description of the invention (1) 1 I Background of the invention 1 I The present invention relates to an alkaline battery which uses m mercury zinc powder as the cathode 1 1 1 active material 9 and uses Silver oxide, manganese dioxide, oxygen, etc. as anode activity 1 I Please 1 | Substances and the use of this. 1? The clock or mine of a human battery. First read 1 I $ 1 I The problem before the giant is the zinc powder used in alkaline batteries The hydrogen gas corroded and dissolved by the electrolyte solution (back 1 1 alkali) and the hydrogen generated in the performance of the battery and the white body in the performance of the battery. Note 1 1 Event 1. The discharge is extremely large. In addition, the collector, such as copper, is in contact with zinc to form the battery. Item 1 Hydrogen is also produced by one another. Methods to prevent the above-mentioned shortcomings in the prior art skills Mercury with high hydrogen overvoltage will amalgamate zinc or add Ά 1 1 I to the electrolyte solution. Slightly saturated zinc oxide 〇1 1 But 9 In recent years, environmental pollution caused by mercury produced by abandoned dry batteries 1 1 People are worried, so they are actively conducting various studies on reducing mercury or reducing mercury. The set 1 includes the formation of alloy collector plating from zinc and the addition of organic or jfrrT: m machine suppression 1 | agent in electrolyte solution 0 1 I zinc alloy formation method has been I have been studying for quite a long time such as bismuth 1, indium > lead and other metals. 0 There are also many patent applications such as Japanese Patent 1 Announcement 2 5 — 2 7 8 2 2 (1 9 5 0) Japanese Patent Announcement 1 3 3 — 3 2 0 4 (1 9 5 8) Japanese Patent Announcement 1 1 6 3 — 3 9 4 2 (1 9 8 8) Japanese Patent Disclosure Case 1 | 1 — 1 0 8 6 1 (1 9 8 9) Wait 〇1 I and most often The jfrrT. The pick-up inhibitors are indium oxide and indium hydroxide, etc. 1 1 I Indium compounds »There are also many patent applications. For example, this patent announcement 1 1 5 1 — 3 6 4 5 0 (1 9 7 6) Japanese patent disclosure request 1 4 9 — 9 3 8 3 1 (1 9 7 4) t Japanese patent disclosure request 1 This paper size is applicable to China National Standard (CNS) A4 (210X29 * 7 Mm) -4-2〇95ϋ A7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of Invention (2) 1 1 4 9 — 1 1 2 1 2 5 (1 9 7 4) Japanese Patent Publication Application 1 I 5 9 — 1 8 6 2 5 5 In the Japanese patent disclosure application 1 I 5 9 — 1 8 6 2 5 6 (1 9 8 4) and the Japanese patent disclosure request 1 case 2 first 1 4 6 0 6 1 (1 9 9 2) 〇While using an earth metal compound 1 1 is Japanese Patent Publication 4 9 _ 8 7 2 7 (1 9 7 4) > back 1 1 of 1 1 Japanese Patent Public case request 4 9 — 9 3 8 3 1 (1 9 7 4) * * Wang Yishi 1 1 This patent case request 4 9 — 1 2 1 9 2 6 (1 9 7 4) etc. ii 1 The organic inhibitor is the Japanese patent disclosure request 2 _ 8 6 0 6 4 (writing page 1 1 9 9 0) The Japanese patent disclosure request 3-2 9 2 7 0 (1 I 1 9 9 1) etc. 〇1 1 I On the other hand, the collector is coated with high hydrogen over-charge 1 1 indium or tin by plating and other methods to prevent contact with zinc to form a battery to produce hydrogen. Generate 0 related patents as Japanese patent disclosure string 1 1 5 2 — 7 4 8 3 4 (1 9 7 7) Japanese patent disclosure string 1 I 5 2 — 9 8 9 2 9 Japanese patent disclosure string Request 6 0 — 2 2 1 9 5 8 (1 9 8 5) Japanese Patent Announcement 1 I 5 2 — 4 2 2 1 1 (1 9 7 7) etc. 0 1 Priority, Body · 刖Skill Art has studied the technologies as described above, but »1 1 has a strong anti-corrosion agent for mercury, so it often fails after understanding the characteristics of each technology 1 | can be the best combination 〇1 I used to prevent corrosion and dissolve mercury in zinc Not only is the cost expensive, but also includes a major problem of environmental pollution. In addition, the addition of zinc oxide also increases the viscosity of the electrolyte. 1 1 »The conductivity decreases. 1 As / rrt. M machine inhibits the M marriage and hydroxide-it Μ also There are many problems 〇1 The paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -5-A7 B7 printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economy V. Invention description (3) Indium oxide is extremely insoluble In the electrolyte solution (caustic), the result is that hydrogen gas is generated due to the contact of indium oxide with zinc powder or collector. Because of the poor solubility of indium oxide, it cannot provide enough indium ions to coat the zinc surface and collector surface, because inevitable impurities in production contact with zinc and collector to make indium oxide conductive, so it is formed Local battery. According to records, compared with indium oxide, indium hydroxide is slightly soluble in caustic electrolyte solution, and its solubility is related to particle size and crystallinity, but it is related to indium compounds such as indium sulfate, indium sulfamate, indium chloride, etc. When comparing, it is extremely difficult to dissolve. Therefore, there are still the same problems as indium oxide. In addition, indium as an amphoteric compound generates poly ions and hydroxyl ions (as described in Inorg-anic Chemistry Series 7, Coordinate Stereochemist-r y, written by Yoichi NI I MURA, published by Baihu-kan Co. Ltd., 65-66 ), And increase the electrolyte concentration, thereby reducing the conductivity of the electrolyte solution and destroying the battery performance. The use of indium compounds that are easily soluble in electrolyte solutions as inhibitors is better than the use of conventionally insoluble inhibitors. However, in order to further utilize the characteristics of the indium compound, the following problems need to be solved. The electrode potential of zinc is lower than the deposition potential of indium, so when indium ions are present in the electrolyte, indium metal is deposited on zinc and the collector in contact with zinc. However, the generation of hydrogen is a competitive reaction of the deposition reaction of indium, so it is a cause of defects such as liquid leakage and expansion of alkaline batteries. In addition, there is another problem that the indium hydroxide precipitate cannot be deposited and the conductivity of the electrolyte solution is reduced. In addition to the indium compound, metal compounds with extremely high hydrogen overvoltage such as tin and lead are used as inhibitors, but the following problems still exist . This paper scale is applicable to China National Atomic Rate (CNS) A4 specification (210'〆297mm) (Please read the notes on the back before filling out this page) Binding · Order-6 Printed by an employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of the invention (4) The metal ions provided by the metal compound of this metal in the electrolyte solution are reduced on the surface of zinc and collector, and the metal is deposited. However, when a metal is coated on the surface, the grains become coarse and the effect is halved. It is difficult to suppress the generation of hydrogen and improve the discharge properties using a single metal. In addition, indium compounds are extremely expensive, so the cost of using only one is high. As far as the corrosion and dissolution of zinc is concerned, it is generally accepted that zinc itself will be corroded by water and hydroxyl groups in the lye, and it will form a local battery in contact with a metal such as copper and brass that is more inert than zinc. Zinc dissolves. Therefore, the most common attempt is to add metals with high oxygen overvoltage to zinc to form alloys to suppress corrosion and dissolution. It is known that the effect when adding indium is particularly significant. When using zinc with a high concentration (for example, not less than 400 p pm) of indium, part of the indium and zinc will dissolve once they come into contact with gold, such as collector copper. It is said that the mechanism in which dissolved indium ions are deposited on the collector and an indium film is formed on the collector inhibits corrosion and dissolution of zinc. However, the problem is that in the initial contact between zinc and the collector, the amount of indium ions reduced on the collector is extremely small, so hydrogen reduction generates hydrogen gas. Such attempts are intended to suppress freshness and use metal compounds with higher inertness than zinc as inhibitors. The most commonly used when the cliff is corroded and dissolved. However, if it is a conventional zinc with a large amount of impurities such as iron, a large amount of inhibitors must be used. Unless, for example, a large amount of lead monoxide, which is non-toxic and potentially polluting the environment, the corrosion and dissolution of zinc cannot be suppressed. In addition, if a large amount of lead monoxide and indium compounds are added, needle-like crystals are deposited, which breaks the separator and causes a short circuit. Secondly, when focusing on the coin-type or button-type silver oxide battery in the battery, the coin-type or button-type silver oxide battery must use mercury. This paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm ) (Please read the precautions on the back before filling in this page) Pack. Order A7 B7 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Invention Description (5) Zinc Zinc 'can avoid the generation of hydrogen and self-discharge And other issues. In recent years, due to efforts to improve additives in zinc powder, separators, sealants, etc., and to change gelling agents, etc., cylindrical alkaline batteries have become unfriendly. However, if it is a coin-type or button-type silver oxide battery that does not have a hydrogen-releasing space due to structural factors, it will not be able to obtain mercury-free batteries due to the problems of self-discharge due to inflation and discharge due to air pressure. At present, the problem of conventional use of inhibitors and water in batteries has been described. Using the improved method, it is possible to obtain those whose alkaline battery characteristics have been considerably improved. However, the defect of removing mercury cannot be satisfied. In addition, the efforts to reach this improved law are detailed below. When only conventional inorganic inhibitors are used, because the amount of electrolyte solution in the real battery is very small, the inhibitor cannot be evenly distributed on the collector and there is no metal coating, or if there are bubbles between the cathode combination agent and the collector, then only This situation occurs when there is no coating of gold. The use of indium and tin, or the electroplating of such metals, is a very effective way of producing and producing collectors. However, when tin is used, the generation of hydrogen gas can be suppressed more than using copper collectors, but the effect of using mercury cannot be achieved. When using indium, although the effect is fixed more than tin, the problem is that the raw materials are expensive, so the cost increases. If indium is electroplated, the problem is that the applicability is poor, a uniform film cannot be formed, impurities remain on the surface, and the effect becomes poor. In addition, when only a metal-coated collector is used without an inhibitor, the problem is not enough to solve the problem of hydrogen gas formation during discharge storage. In addition, even if the organic inhibitors considered to be effective in the prior art are used (please read the notes on the back before filling in this page)

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T This paper scale applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -8 _ A7 __B7___ 5. Description of the invention (6), fluorocarbon / polyoxyethylene series, polyoxyethylene alkylamide etc. It cannot be fully determined that the reduction of self-discharge is completely prevented. That is, it has been found that when the prior art anti-corrosion method is used, a sufficient effect cannot be obtained. Reconsidering the results of the role of each inhibitor, it is found that the collector (coated with zinc or a metal whose hydrogen overvoltage is higher than zinc) and various inhibitors have a better effect. In the case of high capacity, the battery capacity is reduced because of the lack of mercury-free capture. If it is a cylindrical alkaline dry battery, it is necessary to add zinc powder as an active material, but if it is a button-type or coin-type battery with no space, this is almost impossible to complete. On the other hand, in the case of clocks or watches with mercury-containing alkaline batteries, if the batteries are exchanged, the mercury-containing batteries are recovered in retail stores, but the problem is that when the main body of the clock or watch is discarded, the environment is also discarded Of mercury. In particular, as the price of watches or clocks becomes lower, the number of discarded watches or clocks due to the battery life is increasing. "General invention. Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the notes on the back first #Fill in this page) The subject of the present invention is to propose an alkaline battery that does not contain mercury. Another subject of the present invention is a chrysanthemum battery using mercury-free zinc powder as a cathode active material. Another subject of the present invention is to propose a product using mercury-free alkaline batteries. Another subject of the present invention is a product using an alkaline battery which uses mercury-free zinc powder as a cathode active material. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). The A7 _B7 is printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy. V. Description of the invention (7) Adding indium sulfate to the electrolyte solution or cathode active material, ammonia based Indium compounds such as indium acid, indium chloride, etc., when the amount of indium ions in the electrolyte solution is sufficient to coat zinc and collector, then indium can be deposited on zinc and cathode collector immediately. When zinc and collectors are coated with indium with high hydrogen overvoltage, they can be prevented from corrosion and dissolution. In addition, in order to effectively use such inhibitors, a complexing agent is added to the electrolyte solution in advance to dissolve the indium ions generated by the dissolution of the indium compound, thereby solving the formation of hydrogen gas during indium deposition and the deposition of indium non-hydroxide And reduce the problem of the conductivity of the electrolyte solution. The solution to the problem caused by using only one metal compound inhibitor »is to add two or more compounds selected from indium compounds, tin compounds containing tetravalent tin, and lead oxide compounds to the electrolyte solution or cathode active material, and An alloy of metals contained in such compounds is deposited on zinc and the cathode collector. Characteristics that cannot be obtained by coating with a single metal can be obtained by depositing two or more metals. When zinc with an extremely high concentration of indium is used, the mechanism in which the indium ions eluted from zinc are deposited on the collector will inhibit [(zinc Or collector) (corrosion and dissolution)], an indium film is formed on the collector. However, during the initial contact of zinc with the collector, the amount of indium ions reduced on the collector is extremely small. Therefore, one or more compounds selected from indium compounds with higher inertness than zinc, tin compounds containing tetravalent tin, and lead oxide are added to the electrolyte solution or cathode active material as inhibitors, and the metal ions present in the electrolyte solution are added The amount is sufficient to coat zinc and collector, then lead can be immediately deposited on zinc and cathode collector, and the generation of hydrogen can be suppressed. In this case, according to the amount of indium in the zinc powder, it is better to add the Chinese national standard (CNS) A4 specification (210X297mm) relative to the paper size --------- {装 ----- -Subscribe ------ {. · ≫ (»(please read the precautions on the back before filling out this page) 1:10-A7 B7 Central Government Bureau of Economic Affairs Employee consumption cooperation du printing 5. Invention description (8 ) Inhibitor of zinc powder about 1 0 _ 1 0 0 0 PP m. If the added amount is small, the zinc and collector cannot be fully coated, and when the added amount is too large, it will form a needle shape that penetrates the separator Crystallization causes a short circuit. When using iron-free mercury-free zinc powder with a content not greater than 4 p pm relative to the weight of zinc, add one or more inert compounds selected from inerts higher than zinc to the electrolyte solution or cathode active material When tin compounds and tin oxide compounds are used as inhibitors and the amount of ions present in the electrolyte solution is sufficient to coat zinc and collectors, metal coatings with higher inertness than zinc can be deposited on zinc and cathode collectors immediately Film, and can inhibit the corrosion and dissolution of zinc and generate hydrogen. In this case, it is better to add about 1 to zinc powder 0-1 0 0 0 Inhibitor for PP m. If the added amount is small, zinc and collector cannot be fully coated, and needle crystals can penetrate the separator, causing a short circuit. Use contains at least one selected from gallium and indium , Lead, bismuth, aluminum, calcium and other metals (it is said to have the effect of increasing hydrogen overvoltage and the effect of adjusting the shape of particles when producing cathode active materials) mercury-free zinc, if it is a potassium hydroxide type electrolyte solution, the battery The amount of water in it is 0.31-0.57mg (or 0.31-0.57β $ at room temperature) per 1mg of mercury-free zinc, or if it is an electrolyte solution of sodium hydroxide type, then the battery The amount of water is 0.32-0.59 mg (or 0.32-0.59 4 5 at normal temperature) per 1 mg of mercury-free zinc, which is produced in the gas of coin or button-type silver oxide batteries The generated amount is not greater than 0.03 JW g / day, and the self-discharge rate is not greater than 4% / year. In addition, in order to evaluate the performance of mercury-containing batteries, various technologies need to be combined and used. (Please read the precautions on the back first (Fill in this page)

、 1T • tn 1 ^ 1 The paper size is in accordance with Chinese National Standard (CNS) A4 (210X297mm) -11-A7 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of invention (9) Use of indium added , Lead, bismuth, calcium, aluminum and other metals and mercury-free zinc alloy powder used as a gelling agent to maintain the humidity of the battery as the cathode combination agent, the outermost layer is coated with zinc or the collector of the metal whose hydrogen overvoltage is higher than zinc, In addition, an inhibitor selected from indium compounds, lead oxides, alkaline earth metal hydroxides, and surfactants with polyoxyethylene groups is added to the electrolyte solution or the cathode active material, resulting in less hydrogen generated in the battery, and The electrical properties are good. In particular, an alloy layer in which the necessary component is zinc and the selective component is one or more metals selected from indium, lead, and tin is a collector coating, to provide a cost-effective alkalinity that can suppress hydrogen generation battery. In addition, because of the problem of mercury-free self-discharge and reduced capacity, the collector zinc alloy layer can be made thicker to a certain extent, because the battery capacity is increased without changing the battery space too much. Indium compounds such as indium sulfate, indium sulfamate, indium chloride, etc. are dissolved in a concentrated caustic solution, which forms alkali complex ions that can be reduced by cathode in electroplating. The complex ion of the base of indium undergoes zinc surface reduction (the potential is lower than the reduction potential of itself), and indium metal is immediately deposited. In addition, the collector such as copper is in contact with zinc, so it has the same potential as zinc and indium is also deposited. When the zinc and collector surfaces come into contact with indium initially, all surfaces have indium potential and lose the driving force for electrochemistry, so indium stops re-depositing. However, when the zinc surface is initially discharged, the alkali dislocation ionic indium is immediately reduced and deposited. The indium compound inhibitor is more effective by adding a complexing agent. This is due to the instability of the indium complex ions and hydrated indium ions, so no complexing agent precipitates and does not dissolve in the electrolyte solution, or even if it is dissolved, it will sink when the environment changes slightly. The paper standard is applicable to the Chinese National Standard (CNS > A4 specification (210X297mm) _____ -12-(please read the precautions on the back before filling in this page) Binding-Order a copy of the consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs, du printing a ΰ95ϋ8 Α7 Β7 V. Invention description (10 ) Lake (hydroxide), or easily become a viscous polyion solution (the same as Inorganic Chemistry Series 7, Coordinate Stereochemistry, written by Yoichi NIIMURA, published by Baihukan Co. Ltd., 65-66) In addition, the indium base complex ion water and indium ion hydrate are unstable and have a low deposition potential, but the potential range is wide, and hydrogen is also induced during deposition. Therefore, when using tartrate or E DTA for the complex, Stable complex ion is generated, which can narrow the range of indium deposition potential, can be separated by hydrogen deposition potential, and can only deposit indium without generating hydrogen gas. In addition to indium, the separation of tin and lead The tendency of chemical transformation is also less than zinc, so when the ions of such metals exist in the electrolyte solution, such metals can be deposited on the surface of zinc. In addition, because the collector is in contact with zinc, the potential becomes the same as zinc, and the above deposits Metal. However, the function of mixing indium compounds, tin compounds containing tetravalent tin, lead oxide, etc. to further inhibit corrosion and dissolution is not fixed, but the following factors may be considered. One is that such gold is deposited on zinc and An alloy is formed on the collector. During the formation, the crystals of the deposited gold are thinned, and the surface of the zinc and collector is coated with a uniform film without defects. For example, if it is an indium-tin alloy, when the composition is close to 50:50 atoms When the eutectic point of% is low, the crystallinity becomes fine. If it is an alloy with a three-component system, the crystallization is more complicated, preventing the formation of coarse crystal grains, so it is easy to obtain a uniform film. The other is the one that can use each metal at the same time when mixing In particular, if it is lead, if it is used alone, the needle-like crystals are deposited, the surface of zinc and the collector cannot be uniformly coated, and the effect is not great. However, when combining batteries, if the pre-printed paper size is suitable for China Standard (CNS) Α4 specification (210X297mm) (Please read the precautions on the back before filling in this page), installed., 1Τ 13-A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (11) First Add electrolyte solution containing indium compound and tin compound (including tetravalent tin); then add electrolyte solution containing lead oxide, then zinc and collector are coated with indium and tin (forming a very uniform film), and then coated with lead needles Crystallized film. A uniform film of indium and tin suppresses the corrosion and dissolution of zinc or the collector, and a lead film with needle crystals strengthens the electrical contact between the collector and the collector, and improves the shock resistance and discharge performance. Hydrogen cathode active materials such as pure zinc, etc., produce hydrogen gas (competitive reaction of metal deposition on the surface) and the effect of less deposited metal, so it is difficult to form a uniform film. Therefore, if indium, bismuth, lead, aluminum, calcium, gallium, etc. are added to zinc in the cathode active material used, the generation of hydrogen gas can be suppressed appropriately. The most common attempt is to add high hydrogen overvoltage metals to zinc to form alloys to suppress corrosion and dissolution. It is known that the effect when adding indium is particularly significant. When zinc with indium added at a very high concentration, for example, not less than 400 p pm, is in contact with metals such as copper of the collector, the indium and zinc dissolve immediately. The dissolved indium ions are deposited on the collector, and the organization that forms the indium film on the collector is recognized to suppress corrosion and dissolution of zinc. However, during the initial contact between zinc and the collector, the amount of indium ions reduced on the collector is extremely small. Therefore, one or more compounds selected from indium compounds with higher inertness than zinc, tin compounds containing tetravalent tin, and lead oxide compounds are added to the electrolyte solution or cathode active material as inhibitors, so that the amount of metal ions in the electrolyte solution is sufficient When zinc and collector are coated, lead can be deposited on zinc and cathode collector immediately, and the generation of hydrogen can be suppressed. When zinc is rich in iron, there are many places where the iron is exposed to the zinc surface. The zinc and iron on the surface form a local battery in the electrolyte solution, and the zinc dissolves, and the Chinese standard (CNS) Α4 specification (210Χ297mm) is applicable to this paper standard (please read the precautions on the back before filling this page).

、 1T 14-Printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of invention (12) Iron produces hydrogen. Where hydrogen gas is generated, it is difficult to form a suppression coating film, and it is difficult to obtain the effect of an inhibitor. The iron content of the mercury-free zinc powder used is not more than 4 p pm relative to the weight of zinc, and one or more inert compounds selected from inerts higher than zinc, tin compounds containing tetravalent tin and oxidation are added to the electrolyte solution or cathode material When the compound in lead is an inhibitor and the amount of ions in the electrolyte solution is sufficient to coat zinc and collector, a metal film with higher inertness than zinc can be immediately deposited on zinc and the cathode active material, and the corrosion of zinc can be suppressed And the generation of dissolved and accompanying hydrogen. The preferred amount of inhibitor added is about 10 to 100 ppm relative to zinc powder. If the added amount is small, zinc and collector cannot be effectively coated, and the disadvantage is that the needle crystal penetrates the separator, causing a short circuit. It is generally believed that gallium, indium, lead, and bismuth have a high hydrogen overvoltage, and when added to zinc, the generation of hydrogen gas can be suppressed. It is said that aluminum and calcium can be atomized during the production of zinc powder to smooth the surface, reduce the surface area of the zinc powder, and suppress the generation of hydrogen in the same way. In addition, although the function is uncertain, the maximum amount of electrolyte leakage can be achieved. Suppression of hydrogen generation and self-discharge. In addition, increasing the electrolyte solution can also increase the absolute amount of inhibitor used to suppress hydrogen generation and self-discharge, and increase the inhibitor effect. In order to make mercury-free batteries close to the performance of batteries containing zinc amalgam, it is necessary to understand the characteristics of various technologies and combine and use them. The following shows the function of each technology. 8 In general, adding zinc, indium, lead, bismuth, calcium, aluminum, and other gold to prevent corrosion and dissolution and suppress the generation of hydrogen. However, the standard of various papers with added gold is applicable to the Chinese National Standard (CNS) A4 (210X297mm) (please read the precautions on the back before filling in this page). A7 B7 printed by the Bureau ’s Consumer Cooperatives V. Description of the invention (13) The role has changed. Metals with high hydrogen overvoltage, such as indium, lead, and bismuth, form an alloy with zinc, increase the hydrogen overvoltage, and prevent corrosion and dissolution. On the other hand, because calcium and aluminum are atomized during production to smooth the surface of the alloy, the potential distribution is uniform, and the surface area of the zinc particles is reduced, so corrosion and dissolution can be prevented. In addition, when the zinc surface produces hydrogen due to corrosion and dissolution, there is no inhibitor and no inhibitor effect on the zinc surface. In this regard, the addition of the metal of the present invention is extremely important for forming a zinc alloy. The cross-linked polyacrylic acid water-absorbing polymer used as a gelling agent has strong moisture retention, prevents evaporation of the electrolyte solution and unfavorable movement relative to the separator and the anode surface. Therefore, the inhibitor can be fully distributed and the internal resistance can be suppressed The increase (due to the accumulation of fluid in the late stage of discharge). The reason why a zinc layer or a metal layer with a hydrogen overvoltage higher than that of zinc is formed on the outermost layer of the collector is to prevent the mercury-free zinc powder as the cathode active material from contacting the collector copper to form a battery, which also generates hydrogen gas. In addition, when a metal layer with zinc or hydrogen overvoltage higher than zinc is formed after the cathode-containing cathode is processed by pressure, impurities such as iron and the like can be prevented from adhering to the collector surface during processing. Especially at the collector An alloy layer containing the necessary components zinc and one or more selective elements selected from indium, lead and tin is provided on the surface. This is because the collector surface potential is substantially the same as the mercury-free zinc surface as the cathode active material. Therefore, even when the collector is in contact with the mercury-free zinc powder as the cathode active material, the formation of local batteries and the generation of hydrogen can be avoided. It is assumed that even if only zinc electroplating on the collector can make the potential difference disappear and have an effect, but the zinc deposited by electroplating and other methods is extremely active and easy to corrode, so the paper size is applicable to China National Standard (CNS) A4 specification (210X297 Mm) (Please read the precautions on the back before filling out this page)

, 1T -16-A7 B7 printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (14) The effect of hydrogen production is extremely small. Therefore, lead should be added to zinc in an amount of not less than 10 p pm And alloys of indium. In the electroplating method, the electro-ore fluid may need to be added with an indium compound, a lead compound, and a tin compound in the range of 100 to 1000 ppm in a general zinc plating solution, and the anode may be a fresh alloy. For example, if it is a zinc sulfate type plating solution, indium sulfate can be added, and if it is a cyanide type plating solution, indium cyanide can be added. As for inhibitors, there are inorganic and organic types. Among them, inorganic inhibitors are roughly classified into two types. One is a compound of a metal that is more inert than zinc and has a high hydrogen overvoltage. For example, it is the above-mentioned indium compound such as indium sulfate, indium sulfamate, indium chloride, indium hydroxide, etc., and it is dissolved in a concentrated caustic soda solution to form an alkali complex that can perform so-called cathode reduction in electroplating Ions "The indium complex ion of indium is reduced on the surface of zinc whose potential is lower than its own reduction potential, and immediately deposits metal indium. When zinc was coated with indium, all surfaces had the potential of indium and lost the driving force for electrochemistry, so no indium was deposited. However, when the zinc surface is initially exposed by discharge, indium in the form of alkali complex ions is immediately reduced and deposited. Therefore, even when the discharge is stopped halfway and stored, the generated hydrogen gas is still small, and the self-discharge rate is also small. Since the collector (such as copper, etc.) that is in contact with zinc also shows a lower potential than its own reduction potential, the base complex ion of indium is reduced, and indium gold is immediately deposited. However, the amount of electrolyte solution in the actual battery is quite small. Therefore, the inhibitor cannot be evenly distributed on the collector so that there is no metal coating. When there are bubbles between the cathode assembly and the collector, a completely metal-free coating is produced. Therefore, it is impossible to have a sufficient effect. Such inorganic inhibitors include lead monoxide and tetravalent tin compounds. "This paper uses the Chinese National Standard (CNS) A4 specifications (210X297mm) (please read the precautions on the back before filling out this page). 17-A7 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (15) Other inorganic inhibitors are oxides and hydroxides of metals stronger than zinc or non-metallic alkalinity. Although its function is not clear, it has the effect of suppressing the generation of hydrogen gas and improving the electrical properties. Typical examples are barium hydroxide or alkaline earth metal hydroxide. However, when using a zinc-free layer or a collector whose hydrogen overvoltage is higher than the outermost layer of the metal layer of zinc, because the contact between the collector and zinc generates too much hydrogen gas, the effect is minimal. Organic type surfactants have a hydrophilic group attached to the zinc surface and a hydrophobic group inhibits water and hydroxyl groups from approaching the surface, so it can suppress corrosion and dissolution of zinc. The effect is the same as the alkali metal hydroxide. Therefore, it needs to be used in combination with the outermost collector of the metal with zinc or hydrogen overvoltage higher than zinc. In addition, although its function is uncertain, when polyoxyethylene, alkylamide, barium hydroxide, etc. are used in combination, a significant effect of suppressing the generation of hydrogen is obtained. However, organic surfactants have extremely strong adhesion to zinc and the collector surface, and inhibit the reduction of indium compounds or lead monoxide on the surface, so the addition amount needs to be as small as possible to the effective range. It has been found that when zinc or a metal whose hydrogen overvoltage is higher than zinc is coated on the collector, because zinc contacts the collector, the generation of hydrogen gas is suppressed, and indium compounds and lead monoxide suppress self-discharge after partial discharge The hydroxide improves the electrical properties and obtains the greatest effect when used in combination. That is, when using an alkaline battery with a zinc or hydrogen overvoltage that is the outermost layer of the metal produced by the collector, it can be discharged before use and partially After the self-discharge rate is small and the electrical properties are good. When the collector is coated with a zinc alloy, the zinc alloy itself becomes a cathode active material, so the zinc alloy layer is thickened on the collector surface, so it can be added because the mercury-free lack of this paper The standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling in this page)

, 1T 18-A7 B7 5. The battery capacity of the invention description (16). For example, 'When the diameter 6 is plated with 1 〇 # 111 on the collector,' because the specific gravity is 7 · 1 3 ', the amount of cathode active material increases by 2 mg. If the amount of cathode active material (zinc powder) is 30 mg, the capacity can be increased by about 6.7% without changing the battery space too much. However, the surface area is smaller than that of the powdery cathode active material, so a large current cannot be obtained. The value is the most suitable for increasing the battery capacity of the micro discharge such as batteries used in clocks and watches. In addition, the thickening of zinc alloy plating is also beneficial to the processing of battery cans. Generally, a cathode can having a cathode collector is made by punching a ring-shaped material. In this case, if the ring-shaped material surface as the collector is previously coated with a certain thickness of zinc alloy, the probability of exposure of the matrix gold (such as copper) during processing decreases. Brief Description of the Drawings Figure 1 is a graph of the amount of hydrogen produced versus the number of days elapsed. Figure 2 is a graph of the amount of hydrogen gas generated versus the concentration of indium sulfate. Fig. 3 is the current-potential curve in potassium hydroxide solution at normal temperature. Figure 4 is the current-potential curve in a normal temperature potassium hydroxide solution (with nearly saturated zinc oxide dissolved). Figure 5 is a graph of the amount of generated hydrogen versus the number of days passed. Figure 6 is a graph of the amount of generated hydrogen versus the concentration of indium sulfate. Fig. 7 is a graph of the amount of hydrogen gas generated relative to the amount of lead oxide added to the electrolyte solution of the present invention. Fig. 8 is a graph of the amount of hydrogen gas generated relative to the amount of lead oxide added to the electrolyte solution. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (Please read the precautions on the back before filling this page), -0

T Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 19-A7 B7 V. Description of the invention (17) Figure 9 shows the amount of hydrogen produced relative to the amount of water added per 1 mg of zinc when using potassium hydroxide electrolyte solution Figure. Figure 10 is a graph of the amount of hydrogen produced relative to the amount of water added per 1 mg of zinc when using a sodium hydroxide electrolyte solution. Fig. 11 is a graph of the amount of hydrogen produced relative to the number of elapsed days when the inhibitor of the present invention is added to a plated copper plate. Fig. 12 is a graph of the amount of hydrogen gas formed with the elapsed days when the inhibitor of the present invention is added on an electroless copper plate. Fig. 13 is a graph of change in self-discharge rate against inhibitor concentration. Fig. 14 is a graph of the change of self-discharge rate with respect to the inhibitor concentration after 50% deep discharge. "Fig. 15 is the amount of hydrogen gas generated relative to the number of elapsed days when the inhibitor of the present invention is added on a plated copper plate Figure. Fig. 16 is a graph of the amount of hydrogen gas generated with the elapsed days when the inhibitor of the present invention is added to an electroless copper plate. Figure 17 is a graph of the change in self-discharge rate versus inhibitor concentration. Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in this page). Figure 18 shows the discharge at 50% depth A plot of the change in self-discharge rate after the concentration of the inhibitor. Figure 19 is a graph showing the amount of hydrogen gas generated relative to barium hydroxide. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The following reference examples illustrate the invention. The effect of using the indium compound of the present invention is illustrated in Examples 1_3 and Comparative Example 1 »This paper scale is applicable to the Chinese National Standard (CNS) A4 (210X297 mm) -20-A7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs B7 V. Description of the invention (18) < Example 1 > 2 g of zinc powder (containing 5 0 0 p pm each) is pre-added to a special test tube with a volume of 25 m P and a scale to measure the amount of gas generated Bismuth, indium and lead prepared by spray method), and the same material as the collector and a copper sheet with an area of 0.6 cm2 and a thickness of 0.1 mm, add an electrolyte solution for the test and heat to 60 ° C to measure the volume of hydrogen generated _7th. The test was repeated 10 times, and the average value was used as the result. The preparation method of electrolyte solution, if it is potassium hydroxide type, use potassium hydroxide 30% by weight and add zinc oxide to near saturation solution, if it is sodium hydroxide type, use sodium hydroxide 25% by weight and Add zinc oxide to a nearly saturated solution as a matrix, then add the indium compound. Nihon Kagaku Sangyo Co., Ltd., Indium Sulfate, Nihon Kagaku Sangyo Co., Ltd., Indium Amine Basic Acid 35% Solution, Wako Pure Chemical Industries., Ltd., Chlorine Indium cyanide, and indium cyanide manufactured by Ito Phamaceutical Co., Ltd. The indium compound is added to the electrolyte solution. The added amount is 100 ppm. The results are shown in Table 1 for the amount of hydrogen produced. The unit is β L / g / day ° < Comparative Example 1 > The test is the same as Example 1, except that the indium compound of the present invention is not added, and the amount of indium oxide added to the electrolyte solution is 1 0 0 0 p pm Take measurements. Indium oxide manufactured by Kanto Chemical Co., Ltd. was used. The results are also expressed in the amount of hydrogen produced in Table 1. The unit is; a L / g / day * This paper scale is applicable to China National Standard (CNS) A4 specification (210X 297mm) (please read the precautions on the back before filling out this page) 19) Table 1. Comparison of hydrogen generation volume and discharge capacity of experimental batteries The Central Standards Bureau of the Ministry of Economic Affairs, Employee Consumer Cooperative printed the example of the present invention Electrolyte indium compound 100 ppm Hydrogen volume generated ML / g / day Comparison of discharge capacity 1 Κ0Η I nS〇4 indium sulfate 24. 29 102 2 Κ0Η In (NH2S〇3) 3 indium sulfamate 30.5 1 102 3 Κ0Η indium chloride 35.40 101 4 Κ0Η indium cyanide 20.66 103 5 NaOH I nS〇4 indium sulfate 18.11 102 6 NaOH In (NH2S〇3) 3 Indium Aminosulfonate 27.43 102 7 NaOH Indium Chloride 29.67 102 8 NaOH Indium Vaporization 14.21 103 Comparative Example 9 KOH — 516.63 100 10 KOH M3M 196. 10 97 11 NaOH — 420.36 100 12 NaOH indium oxide 150.88 97 The paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X 297 mm) (please read the precautions on the back before filling this page) $ Γ -22-Central Bureau of Economics and Trade Beta : A 7 B printed by industrial and consumer cooperatives 7 5. Description of the invention (20) Figure 1 shows a graph of the amount of hydrogen produced relative to the number of test days of the sample when using an electrolyte solution of the potassium hydroxide series. It has been found that those without the addition of indium compounds are shown in Fig. 1, and the amount of hydrogen generation increases exponentially with respect to the number of test days. It is known that the addition of the indium compound (indium sulfate) of the present invention in Fig. 2 suppresses the generation of hydrogen gas. If indium oxide is added as shown in Figure 3, more hydrogen is generated in the first half. It is recognized that because of the poor solubility of indium oxide, the supply of indium ions to the electrolyte solution is insufficient, and it takes a long time to coat the surfaces of zinc and copper. In addition, it is recognized that the reason for the poorer results in the first half compared with those without additives is that indium oxide also contacts zinc and the collector to form a local battery. Indium cyanide shows good properties, but it may not need to be used because it may have new pollution problems. < Example 2 > A part of the electrolyte solution and 116 mg added to the anode can were added to the anode pellets, and the molded tablets (silver oxide content 98%) were placed, and a polyethylene separator and cellophane were placed Clapboard. Secondly, push the nylon pad into the anode tank, add penetrant, gelling agent, 30 mg zinc powder, inhibitor, etc., add the remaining electrolyte solution drop by drop, and place the cathode seal to produce 100 various buttons Type silver oxide battery. Using the same zinc solution as in Example 1 and the electrolytic solution in Table 1, the size of the battery produced was the same as that of the SR6 2 1 type. However, the amount of indium added relative to the amount of zinc is 100 ppm. The results are shown in the discharge index in Table 1. The discharge characteristics are measured using a 2 Ο Ω resistance. The DC method is used when the electrolyte solution is potassium hydroxide series, or the pulse method is used when it is sodium hydroxide. In all cases, no inhibitors are added. The paper size applies to the Chinese National Standard (CNS) A4 specification (210 '297 mm) (please read the precautions on the back before filling this page),-° -23-Economy A7 B7 is printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau. V. Invention Instructions (21) All of them regard their discharge index as 100. As shown in the results, it has been found that the indium compound of the present invention also has discharge characteristics. < Example 3 > Using the method of Example 2, a button-type silver oxide battery using a polypropylene gasket permeable to hydrogen was prepared. Place 10 silver oxide batteries made in a glass container in a high-temperature bath filled with liquid paraffin, attach a graduated collection tube at the top, and measure the amount of hydrogen produced. This state is maintained at 60 ° C for 20 days (it is said to be approximately equivalent to one year), and the amount of hydrogen generated after 20 days is evaluated. As for inhibitors, indium sulfate with a weight of 10 p pm relative to zinc was used for evaluation. The evaluation results are shown in Figure 2. According to this graph, the known effective concentration of inhibitors is 100 p pm to 1%. The polypropylene gasket is replaced by those made of nylon, and the button-type silver oxide battery is produced in the range of indium sulfate concentration of 100 P pm to 1%. At this time, little gas is generated. Similarly, 10 batteries were placed in a glass container filled with liquid paraffin in a high-temperature bath at 25 ° C, and a collecting tube for collecting hydrogen was attached to the top. No hydrogen was found after 60 days at 60 ° C, the tank swelled and liquid leaked. The effective concentration of indium sulfate is 100 ppm to 1% (relative to zinc). However, by adjusting the molar number and determining the concentration range, other indium compounds can have the same effect. When the battery was actually trial-produced, the value generated was less than the amount of hydrogen generated in the experiment of Example 1. Based on this fact, it is recognized that the copper sheet structure used in Example 1 is different from the actual collector, and the hydrogen generated is partially consumed by the reduction of silver oxide. The amount of hydrogen generated by the method of Example 1 is different, but it is sufficient to observe and predict the original paper. Standards apply to China National Standards (CNS) A4 (210X297mm) (Please read the notes on the back before filling this page) 4 ° Λ -24-A7 B7 printed by the Employee Consumer Cooperative of the Central Bureau of Standards, Ministry of Economic Affairs DESCRIPTION OF THE INVENTION (22) »A method of replacing the characteristics of hydrogen produced in a battery. According to Examples 4 to 7, the effect of using the indium compound and the complexing agent of the present invention will be described. < Example 4 > 30% potassium hydroxide electrolyte solution, using 1 cri platinum electrode as the operating electrode, the same method using 1 cri platinum electrode as the counter electrode, and using a comparative electrode manufactured by Toa Electronics Ltd • HC-2 0 5 C is the reference electrode and determines the current-potential curve during indium deposition. The potential is scanned from the positive terminal to the negative terminal at a speed of 10 OmV / s e c. The current at each potential shows the reaction of the electrode. For example, if a reduction reaction occurs such as indium deposition and the generation of hydrogen gas, it causes a current. The results are shown in Figure 3. 1 in the figure is 0.1 mO indium sulfamate added to the electrolyte solution. In this case, the current begins to flow at a point of 1. IV relative to the reference electrode, indium is deposited and hydrogen is generated at the same time. 2 The current-potential curve obtained by adding 0.1 lm〇5 / L potassium tartrate to the electrolyte solution and then adding 0.1 lm〇P / L indium sulfamate is known to deposit indium at about 1.4 V, and Hydrogen is produced at about -2.0V. It is recognized that because indium with a high hydrogen overvoltage is deposited on the electrode surface, the potential for generating hydrogen gas moves to the negative terminal. Therefore, the deposition potential of indium can be separated from the potential of generating hydrogen gas. If indium is deposited first, it is a recognized fact that the amount of hydrogen produced is smaller. If indium sulfamate and potassium tartrate are added to the electrolyte solution, when indium sulfamate is added first, indium hydroxide and poly ions are generated and become turbid, but when potassium tartrate is added first, the paper scale applies to the Chinese national standard ( CNS) A4 specification (210X297mm) --------- (install ------ order ------ ί i (please read the precautions on the back before filling this page) -25 -Printed by the Ministry of Economic Affairs, Central Bureau of Standards, Employee and Consumer Cooperative A7 B7 V. The description of the invention (23) is not turbid. Figure 3-3 shows the addition of 0 · lmop / L indium aminosulfonate to the electrolyte solution, then 0 · lmoj ? / L Potassium tartrate current-potential curve. In the figure, there may be a small spike caused by indium near _1.4V, but, as in the case of not adding potassium tartrate, it is near _1.IV relative to the reference electrode ， Indium is deposited, hydrogen is generated at the same time, and the effect of adding a complexing agent is reduced. In the same way as other indium compounds and complexing agents, in order to immediately form indium complexing ions and prevent precipitation, the complexing agent needs to be dissolved in the electrolyte solution first. ; Example 5 > 30% by weight of potassium hydroxide electrolyte solution (added Zinc oxide to near saturation), using the lciri platinum electrode as the operating electrode, also using the 1 cm pin electrode as the counting electrode, and using the comparison electrode HC — 2 0 5 C made by Toa Electronics Ltd. as the reference electrode, decided Current-potential curve during indium deposition. The results are shown in Table 4. In the figure, 4 is the addition of 0.1 m 〇j · / L indium sulfamate to the electrolyte solution, which is a 1.56V relative to the reference electrode. When the metal is deposited, hydrogen is generated at the same time. The metal deposition potential is lower than that without zinc oxide, so it may be an alloy of zinc and indium. 〇5 is added to the electrolyte solution. The current-potential curve under the condition of 0 _ lmoi / L indium sulfamate. There is a peak known as indium deposition near 1.5V, and then the metal is deposited at about -1.56V, and hydrogen is generated at the same time. The size of the paper is applicable to the Chinese National Standard (CNS) Μ specifications (210X297 mm) (please read the precautions on the back before filling in this page) -'β -26-A7 B7_5 printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 2. Description of invention (24) Recognized at about 1. 5V of the deposited substance, the potential is kept at 1.5V for 30 seconds, and the deposited metal is immersed in nitric acid. If it is zinc, it should be dissolved immediately, but it is difficult to dissolve, so it is assumed that the deposit is indium or contains A large number of indium alloys. The measurement result shows that the potential of the zinc electrode relative to the reference electrode is a 1.59 V. This corresponds to the potential of only indium or an alloy with a large amount of indium deposited in a solution containing a complexing agent. Indium or alloys with a large amount of indium are deposited on zinc and the collector in contact with zinc, which can prevent corrosion and dissolution of zinc and collector. < Example 6 > 2 g of zinc powder (containing bismuth, indium and lead prepared by spray method at 500 Ppm each) was pre-added to a special test tube of volume 2 and scaled to measure the amount of gas generated , And a collector material copper sheet with an area of 0.6 cma and a thickness of 0.1 lram, adding an electrolyte solution for the test and heating to 60 ° C. The volume of hydrogen gas produced is measured for 7 days. The test was repeated 10 times and the average value was used as the result. The preparation method of electrolyte solution, if it is potassium hydroxide series, add about saturation in 30% potassium hydroxide solution .. zinc oxide, if it is sodium hydroxide series, in 25% heavy sodium hydroxide solution Add approximately saturated zinc oxide as a matrix, and add the complexing agent and indium compound. Indium sulfate made by Nihon Kagaku Sangyo Co., Ltd., 35% indium amine basic acid solution made by Nihon Kagaku Sangyo Co., Ltd., and indium chloride made by Wako Pure Chemical Industries., Ltd., And Ito Phamaceutical Co., Ltd.'s gasification paper standard is applicable to China National Standard (CNS) A4 specification (210X 297mm) (please read the precautions on the back before filling in this page) 袈. End -27- Α7 Β7 5. Description of the invention (25) Indium. The added amount of the indium compound is 100,000 ppm relative to the electrolyte solution, and the added amount of the complexing agent exceeds twice the molar ratio of indium ions. The results of adding the indium compound without adding the complexing agent are shown in Table 2. The amount of hydrogen gas produced when the complexing agent is added is shown in Table 3. Hydrogen_production_production index. . When observing the amount of generated hydrogen, it is estimated from the current-potential curve that it is known that the generation of hydrogen is suppressed. Although the cyanide series is also effective, cyanide may have pollution problems, so it is not safe to use "(please read the precautions on the back before filling this page) t · -9

T Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

A7 B V. Description of the invention (26) Table 2. Comparison of hydrogen release volume without complexing agent and discharge capacity of experimental battery. Examples of inventions printed by the Ministry of Economic Affairs Central Bureau of Standards Employees Consumer Cooperatives. Release volume ML / g / day Comparison of discharge capacity 1 K0H indium sulfate — 24. 29 100 2 K0H indium sulfamate — 30.51 100 3 K0H indium chloride — 35.40 100 4 K0H indium cyanide — 20. 66 100 5 NaOH indium sulfate ~ 18.11 100 6 NaOH indium sulfamate — 27. 43 100 7 NaOH indium chloride — 29.67 100 8 NaOH indium cyanide — 14.21 100 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (21 OX 297 Mm) (Please read the notes on the back before filling in this tribute)

bL 、 \ s ° -29-5 3 shows that Yi Yi is real

AB Tong Rong Fang's pool is verified and compared with Tong Rong's hydrogen-releasing agent combined with the misinterpretation of the chemical substance and indium ftay d / g out of the ulcer / the amount of electricity is lower than that of the R-specific acid sulfoamine indium potassium acid tartaric acid Sulfonamide Indium Sodium Tartrate Intarate (Please read the notes on the back before filling this page)

ATD, ιτ acid sulfonamide indium. Acid sulfonamide indium sulfonamide indium acid sulfonamide indium potassium cyanide sodium cyanide printed by the employee consumer cooperative of the Central Standards Bureau of the Ministry of Economy ) A4 specification (210X 29 "? Mm) -30-A7 B7 printed by the employee consumer cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (28) Add part of the electrolyte solution and 116 mg to the anode canister to add the combination agent to The pellets (silver oxide content 98%) molded in silver oxide are placed with polyethylene separator and cellophane separator. Secondly, push the nylon pad into the anode tank, add penetrant, gelling agent, 30 mg zinc powder, inhibitor, etc., add the remaining electrolyte solution drop by drop, and place the cathode seal to produce 100 various buttons Type silver oxide battery. Using the same zinc solution as in Example 6 and the electrolytic solution in Table 2, the size of the fabricated battery was the same as that of S R 6 21 type. However, the added amount of indium relative to the amount of zinc is 100 ppm, and the added amount of the complexing agent is twice the molar ratio of indium ions. The discharge characteristic is measured using a 2 Ο Ω resistance. The DC method is used when the electrolyte solution is potassium hydroxide series, or the pulse method is used when it is sodium hydroxide. In all cases, those who did not add the complexing agent regarded the discharge index as 100. The results are shown in Table 2 in terms of discharge index. However, the effect of glycine is extremely small, and all test complexes are effective. Based on the above representative examples of indium compounds and complexing agents, if the current-potential curve is determined in the manner of Examples 4 and 5, the effects of the indium compounds and complexing agents can be easily determined. Therefore, other indium compounds and complexing agents having the same effect can also be applied to the present invention. In addition, examples of silver batteries have been described in Example 4, but even alkaline manganese batteries using zinc, air batteries, etc. have the same effect. In addition, if it is a cathode active material with a large amount of generated hydrogen, such as pure zinc, etc., since hydrogen gas that competes with indium deposition is generated on the surface, it is difficult to form a uniform film, so the effect of indium deposition becomes small. Therefore, indium, bismuth, lead, aluminum, gallium, calcium, etc. can be added to zinc to suppress the generation of hydrogen gas to a certain extent. This paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please first Read the precautions on the back and then fill out this page) Binding · Order -31-A7 __B7 j cathode active material with clear instructions (29) printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. \ ^ In Example 8-11, it is explained that the use of a tin compound containing lead tetravalent tin and lead oxide from an indium compound is the effect of the present invention. < Example 8 > In a special test tube with a volume of 25 m J? and a scale to know the amount of gas produced, 2 g of fresh labor (containing bismuth'indium prepared by spray method at 500 ppm each and Lead), and a copper sheet with the same material as the collector and an area of 0.6 cm2 and a thickness of 0.1 mm. Add the test electrolyte solution and heat to 60 ° C. The volume of hydrogen produced is measured for 17 days. The test was repeated 10 times, and the average value was used as the result. The preparation method of the electrolyte solution is, if it is a potassium hydroxide system, add near-saturated zinc oxide to the 30% potassium hydroxide solution, if it is a sodium hydroxide series, add it to the 25% sodium hydroxide solution Nearly saturated zinc oxide is used as a matrix, and it is added with a compound selected from the group consisting of thiomenium, indium sulfonate, indium tin oxide and lead oxide. Indium sulfate and sodium stannate made by Nihon Kagaku Sangyo Co., Ltd., 35% indium sulfamate solution made by Nihon Kagaku Sangyo Co., Ltd., and made by Wako Pure Chemical, Ltd. The amount of lead oxide added to the electrolyte solution is .1.0.0 0 BD..m. The results are shown in Table 4 as the amount of hydrogen generated. The size of this paper is applicable to the Chinese National Standard (CNS) A4 (210X297mm) -------- {装 装 -------- 定 ------ {| (Please read the notes on the back first Please fill in this page again) -32-

7 7 A B V. Description of the invention (30)

/ A Printed by the Employees Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

Table 4. Comparison of Hydrogen Release Volume and Discharge Capacity of Experimental Cells Inventive Example Indium Sulfate Compound Adding Indium Amino Sulfosulfonate Amount of Lead Oxide Sodium Tin Oxide Electrolyte Copper Pieces Immersed in Electrolyte Hydrogen Release Amount H / g / day discharge capacity comparison 1 1000 ΚΟΗ 0 37. 86 — 2 1000 ΚΟΗ 0 27. 14 — 3 ΚΟΗ 0 457.-36 — 4 1000 ΚΟΗ 0 26.81 1 5 1000 ΚΟΗ 5 24.29 102 6 1000 ΚΟΗ 5 30.51 102 7 _ ΚΟΗ on ..55, 5fi 103 8 1000 ΚΟΗ 5 39. 15 101 9 -500 ^ QSL ΚΟΗ 5? Λ 43 103 10 500 500 ΚΟΗ 5 35.71 102 11 500 500 ΚΟΗ 5 50.00 103 12 500 500 ΚΟΗ 5 18.57 103 13 500 500 ΚΟΗ 5 46,43 102 14 333 333 333 ΚΟΗ 5 42.86 103 15 333 333 333 ΚΟΗ 5 42.86 103 16 1000 NaOH 0 35.26 — 17 1000 NaOH 0 23.85 — 18 ΛΜϋ NaOH 0 103.45-19 1000 NaOH 0 24. 17 — 20 1000 NaOH 5 22.14 102 21 1000 NaOH 5 27.51 102 22 1000 NaOH Λ 48.23 103 23 1000 NaOH 5 35. 12 101 24 500 500 NaOH 5 αβ. 82 100 25 500 500 NaOH 5 31, 48 J02 26 500 500 NaOH 5 44.-22 103 27 500 500 NaOH 5 16.11 103 28 500 500 NaOH 5 39.64 102 29 333 333 333 NaOH 5 37. 26 103 30 333 333 333 NaOH 5 35. 12 103 31 < ·-KOH 5 ^ 6, _63_ li) (L (Please read the precautions on the back before filling in this page) Sound-

L, τ Γ This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) -33-A 7 B7 5. Invention description (31) For comparison, the same as the experiment of Example 8 without adding copper plate The experimental results are shown in Table 1-4 and 1-6_19. In addition, the result of not adding the compound is shown in 31 of Table 4. The amount of hydrogen gas generated by 3 1 in Table 4 and 1 2 in Table 4 with respect to the number of test days (combining indium sulfamate and lead oxide with a small amount of gas generated) is shown in FIG. 5. It has been known that the hydrogen production is not produced when the Beiyihe is not added _. Shengqianzu is more irritating to the test day-number J, and if indium amine sulfonate and oxidized agriculture are added, the gas and stimulation are produced . As shown by the data of 3 and 4 in Table 4, lead oxide produces a considerable amount of hydrogen. This is because when lead deposits, needle-like crystals are generated, so the zinc and collector surfaces cannot be uniformly coated. As far as the composition m is concerned, it is known that the i-compound and the oxidation_ship ^ .search.1 "can suppress the generation of hydrogen and improve the discharge characteristics. &lt; Example 9 &gt; Printed by the Consumer Labor Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) Add some electrolyte solution and 1 16mg to the anode can to add the combination agent to the silver oxide The pellets (silver oxide content 98%) molded in the middle are placed with polyethylene separator and cellophane separator. Secondly, push the nylon pad into the anode tank, add penetrant, gelling agent, 30 mg zinc powder, inhibitor, etc., and add the rest of the electrolyte solution drop by drop. Compounds of indium sulfonate, sodium stannate and lead oxide, and placed in a cathode seal to produce 100 various button-type silver oxide batteries. Using the same zinc solution as in Example 8 and the electrolyte solution in Table 4, the size of the resulting battery was the same as that of SR621. However, the compound addition amount relative to the zinc amount is 100 0 0 P pm »The results are shown in the discharge index in Table 4. The discharge characteristics are measured using a 2 Ο Ω resistance. When the electrolyte solution is potassium hydroxide, the paper size is based on the China National Standard (CNS) A4 specification (210X297 mm) -34 — A7 A7 Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Print B7 5. Description of invention (32) Use DC method when using series or pulse method when using sodium hydroxide. In all cases, those who did not add inhibitors regarded the discharge index as 100. As shown in the results, it has been found that the present invention also has discharge characteristics. In particular, the electrical index of those who added the oxidation boat is better than that, because the electrical contact of the needle crystal I has been improved. As far as the composition is concerned, the combination of indium compounds ~, and oxygen is effective, can suppress-produce-hydrogen production name, and improve discharge Chu Sheng. It is inferred that Gu suppresses the production of zinc and the gas produced by the collector, while the enemy _ is politically good-electricity _ special _ &. <Example 1 〇> Using the method of Example 9, a button-type silver oxide battery using a polypropylene gasket permeable to hydrogen was prepared. Place 10 silver oxide batteries made in a glass container in a high-temperature bath filled with liquid paraffin, attach a graduated collection tube at the top, and measure the amount of hydrogen produced. This state is maintained at 60 ° C for 20 days (it is said to be approximately equivalent to one year), and the amount of hydrogen generated after 20 days is evaluated. As for the added compound, indium sulfate and lead oxide (weight ratio 1: 1) with a total concentration of 10 ppm to 5% relative to the weight of zinc are used for evaluation. The evaluation results are shown in Figure 6. According to the graph, it is known that the effective concentration of the added compound is 50 ppm to 1%. The polypropylene gasket is replaced by those made of nylon, and the button-type silver oxide battery is produced in the range of indium sulfate and lead oxide with a concentration of 50 p pm to 1%, and little gas is generated at this time. Similarly, 10 batteries were placed in a glass container filled with liquid paraffin in a high-temperature bath at 60 ° C, and a collecting tube for collecting hydrogen gas was attached to the top. No hydrogen is found after 60 days at 60 ° C. The paper size of the tank is applicable to the Chinese National Standard (CNS) A4 (21〇X297). (Please read the precautions on the back and fill in this page) Order- 35-Printed Α7 Β7 by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (33) Body swelling and liquid leakage. The effective concentration of indium sulfate and lead oxide is 50 p pm to 1%, but, by adjusting The number of ears and the determination of the concentration range can also make other compound compositions have the same effect. When the actual trial battery was produced, the value produced was less than the amount of hydrogen produced in the experiment of Example 8. Based on this fact, it is recognized that the copper sheet used in Example 8 The structure is different from the actual collector, and the generated hydrogen is partially consumed by the reduction of silver oxide. The amount of hydrogen generated by the method of Example 8 is different, but it is sufficient to observe the method of predicting the substitution characteristics of hydrogen generated in a real battery. 1 1 &gt; Using a polypropylene gasket made of hydrogen permeable as in Example 9, a button-type silver oxide battery was produced. However, two electrolyte solutions of 50 p pm relative to zinc were prepared, indium sulfate and oxygen Lead is added in two changes in sequence. The button-shaped silver oxide battery produced was tested at 60 ° C for 20 days in the manner of Example 9. The hydrogen generation amount of the first added indium sulfate was 0 · 1 0 // L / g / day, and the first to add lead oxide is Ο · 15; wL / g / day. The result shows that the effect of adding indium sulfate first to hydrogen gas is greater ^ According to Examples 1 2- 1 4, it shows that the use of indium-containing The effect of zinc and one or more compounds selected from indium compounds, tin compounds containing tetravalent tin and lead oxide (as the inhibitor of the present invention). &Lt; Example 1 2 &gt; At a volume of 25 mj2 and a scale to know the gas generation The size of the special test tube paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the precautions on the back before filling this page).

, 1T -36-A7 B7 5. Description of invention () 34 pre-add 2 g of zinc powder (containing indium of each 500 Ppm) prepared by spray method, and the area of 0.6cnf and thickness of 0.1mm Copper sheet with the same polar material, add test electrolyte solution and heat to 60 ° C, and measure the volume of generated hydrogen for 7 days. The test was repeated 10 times, and the average value was used as the result. The preparation method of the electrolyte solution is that if it is a potassium hydroxide system, Bayi IJ adds near-saturated zinc oxide to a 30% potassium hydroxide solution, and if it is a sodium hydroxide series, it is added to a 25% sodium hydroxide solution Nearly saturated zinc oxide is added as a matrix, and the inhibitor of the present invention such as lead monoxide is added. Table 5 shows the values of the amount of indium added in the zinc powder and the amount of hydrogen generated relative to the amount of lead monoxide added. The amount of lead monoxide added is expressed in p pm relative to the electrolyte solution. The results of hydrogen generation are also shown in Table 5. (Please read the precautions on the back before filling in this page) -s The paper standard printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is applicable to the Chinese National Standard (CNS) A4 (210X297mm) Description of the invention (35) Printed by the Consumers ’Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Hydrogen gas produced by zinc powder Experiment No. Content of indium contained in electrolyte zinc powder ppm Pb 0 in the electrolyte. Zhen ML / g / day 1 Κ 0 Η 2 0 0 0 6 0 3. 3 1 2 Κ 0 Η 2 0 0 10 3 9 8. 8 8 3 Κ 0 Η 2 0 0 5 0 10 2. 56 4 Κ 0 Η 2 0 0 10 0 14.29 5 Κ 0 Η 2 0 0 5 0 0 8 7.01 6 Κ 0 Η 2 0 0 10 0 0 10 5. 70 7 Κ 0 Η 2 0 0 5 0 0 0 12 2.43 8 Κ 0 Η 5 0 0 0 5 16. 92 9 Κ 0 Η 5 0 0 10 3 0.01 10 Κ 0 Η 5 0 0 5 0 2 0.13 11 Κ 0 Η 5 0 0 10 0 6.21 12 Κ 0 Η 5 0 0 5 0 0 14.73 13 Κ 0 Η 5 0 0 10 0 0 4 0.56 14 Κ 0 Η 5 0 0 5 0 0 0 14 3.32 15 Κ 0 Η 18 0 0 0 9 9.21 16 Κ 0 Η 18 0 0 10 10.05 17 Κ 0 Η 18 0 0 5 0 5.33 18 Κ 0 Η 18 0 0 10 0 5.05 19 Κ 0 Η 18 0 0 5 0 0 10.11 2 0 Κ 0 Η 18 0 0 10 0 0 3 1.01 2 1 Κ 0 Η 18 0 0 5 0 0 0 14 2.58 2 2 Ν a 0 Η 2 0 0 0 5 5.01 2 3 Ν a 0 Η 2 0 0 10 3 2 7.3 8 2 4 Ν a 0 Η 2 0 0 5 0 7 0.25 2 5 Ν a 0 Η 2 0 0 10 0 10.67 2 6 Ν a 0 Η 2 0 0 5 0 0 6 2.98 2 7 Ν a 0 Η 2 0 0 10 0 0 8 5.22 2 8 Ν a 0 Η 2 0 0 5 0 0 0 110. 12 2 9 Ν a 0 Η 5 0 0 0 5 0 1. 3 9 3 0 Ν a 0 Η 5 0 0 10 2 5.52 3 1 Ν a 0 Η 5 0 0 5 0 16.33 3 2 Ν a 0 Η 5 0 0 10 0 3.99 3 3 Ν a 0 Η 5 0 0 5 0 0 9.63 3 4 Ν a 0 Η 5 0 0 10 0 0 2 5.42 3 5 Ν a 0 Η 5 0 0 5 0 0 0 10 3.44 3 6 Ν a 0 Η 18 0 0 0 8 2.54 3 7 Ν a 0 Η 18 0 0 10 10.11 3 8 Ν a 0 Η 18 0 0 5 0 4.87 3 9 Ν a 0 Η 18 0 0 10 0 4.51 4 0 Ν a 0 Η 18 0 0 5 0 0 8.73 4 1 Ν a 0 Η 18 0 0 10 0 0 2 4.42 4 2 Ν a 0 Η 18 0 0 5 0 0 0 12 1.12 { Install-(please read the notes on the back before filling this page)

、 1T This paper scale is applicable to Chinese national standard (CNS> A4 specification (210X297mm) -38-A7 B7 printed by the employee consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention description (36) Among the electrolyte solutions of potassium hydroxide series The result of hydrogen generation is shown in Fig. 7 * 1 in the figure is the case of using zinc powder with the addition of 2 0 0 p pm indium, while adding about 1 0 0 — 4 0 0 p pm lead oxide has the effect of suppressing the generation of hydrogen. 2 is In the case of using zinc powder with addition of 5 0 0 p pm indium, and the addition of lead monoxide is not less than 10 PP m, it has the effect of suppressing the generation of hydrogen. 3 is the use of zinc powder with addition of 1 8 0 0 pm pm indium. In the case of the same concentration range, it is effective when the concentration range is 2. Especially when adding high concentration of indium, the effect of the addition of lead monoxide is not more than 100 P pm, so it can reduce the amount of environmental pollutant lead. "& Lt Example Γ 3 &gt; A part of the electrolyte solution and 116 mg added to the anode can were added to the silver oxide molded pellets (silver oxide content 98%), and a polyethylene separator and cellophane were placed Separator. Secondly, push nylon padding into the anode tank and add penetrant Gelling agent, 30mg zinc powder, inhibitors, etc., add the remaining electrolyte solution drop by drop, and place the cathode to seal to produce 100 various button-type silver oxide batteries. The battery size is the same as SR6 2 1. The electrolyte solution is prepared The amount of lead monoxide added is the amount of zinc. Storage at 60 ° C for 20 days, the measurement results of the self-discharge rate are shown in Table 6. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) (please Read the precautions on the back before filling in this page) Fifth, the description of the invention (37) A7 B7 Printed form 6 of the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs • Battery self-discharge rate and hydrogen release rate experiment number Electrolyte zinc powder Indium is removed in ppm. Pb 0 is added to the electrolyte. (P b 0 weight to zinc weight) ppm Self-discharge rate% 1 ML of ML / g / day 1 Κ 0 Η 2 0 0 0 12.1 1.23 2 Κ 0 Η 2 0 0 10 9. 9 0.95 3 Κ 0 Η 2 0 0 5 0 7. 4 0.88 4 Κ 0 Η 2 0 0 10 0 4. 1 0.50 5 Κ 0 Η 2 0 0 5 0 0 8. 7 0.71 6 Κ 0 Η 2 0 0 10 0 0 9. 1 0.91 7 Κ 0 Η 2 0 0 5 0 0 0 15.8 1.56 8 Κ 0 Η 5 0 0 0 11.2 1.11 9 Κ 0 Η 5 0 0 10 4. 2 0.56 10 Κ 0 Η 5 0 0 5 0 3. 5 0.41 11 Κ 0 Η 5 0 0 10 0 2. 5 0.35 12 Κ 0 Η 5 0 0 5 0 0 2. 9 0.32 13 Κ 0 Η 5 0 0 10 0 0 3. 6 0.47 14 Κ 0 Η 5 0 0 5 0 0 0 18.9 1.49 15 Κ 0 Η 18 0 0 0 10.3 1.02 16 Κ 0 Η 18 0 0 10 2. 2 0.30 1 7 Κ 0 Η 18 0 0 5 0 1. 7 0.25 18 Κ 0 Η 18 0 0 10 0 1. 5 0.22 19 Κ 0 Η 18 0 0 5 0 0 2. 1 0.28 2 0 Κ 0 Η 18 0 0 10 0 0 3. 7 0.39 2 1 Κ 0 Η 18 0 0 5 0 0 0 16.6 1.70 2 2 Ν a 0 Η 2 0 0 0 10.3 1.15 2 3 Ν a 0 Η 2 0 0 10 8. 2 0.90 2 4 Ν a 0 Η 2 0 0 5 0 6. 5 0.74 2 5 Ν a 0 Η 2 0 0 10 0 3. 3 0.42 2 6 Ν a 0 Η 2 0 0 5 0 0 7. 5 0.72 2 7 Ν a 0 Η 2 0 0 10 0 0 8. 1 0.86 2 8 Ν a 0 Η 2 0 0 5 0 0 0 13.2 1.35 2 9 Ν a 0 Η 5 0 0 0 10.2 1.00 3 0 Ν a 0 Η 5 0 0 10 4. 0 0.44 3 1 Ν a 0 Η 5 0 0 5 0 2. 9 0.32 3 2 Ν a 0 Η 5 0 0 10 0 2. 2 0.30 3 3 Ν a 0 Η 5 0 0 5 0 0 2 3 0.29 3 4 Ν a 0 Η 5 0 0 10 0 0 3. 1 0.48 3 5 Ν a 0 Η 5 0 0 5 0 0 0 16.7 1.38 3 6 Ν a 0 Η 18 0 0 0 8. 9 0.90 3 7 Ν a 0 Η 18 0 0 10 1. 9 0.31 3 8 Ν a 0 Η 18 0 0 5 0 1. 3 0.21 3 9 Ν a 0 Η 18 0 0 10 0 0. 9 0.19 4 0 Ν a 0 Η 18 0 0 5 0 0 1 . 5 0.25 4 1 Ν a 0 Η 18 0 0 10 0 0 2. 9 0.33 4 2 Ν a 0 Η 18 0 0 5 0 0 0 12.3 1.54 (binding {(please read the precautions on the back before filling this page) This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) -40-Printed by A7 _B7______ by the Employees ’Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Description of the invention (38) 5 0 0 P pm zinc powder of indium, then 1 0 0_ 1 0 0 0 p pm One of the lead oxide additions can suppress the reduction of battery capacity. If it is 1 800 0 ppm indium zinc powder, then 1 0 1 1 0 0 0 P pm-Lead oxide is enough. The reduction in battery capacity when high concentrations of lead monoxide are added is due to the formation of needle-like crystals of lead when excessively added, which may cause a short circuit. &lt; Example 1 4 &gt; Using the method of Example 1 3, a button-type silver oxide battery using a polypropylene gasket permeable to hydrogen was prepared. Place 10 silver oxide batteries prepared in a high-temperature bath in a glass container filled with liquid paraffin, attach a graduated collecting tube at the top, and measure the amount of hydrogen produced. This state is maintained at 60 ° C for 20 days (it is said to be approximately equivalent to one year), and the amount of hydrogen generated after 20 days is evaluated. The results are shown in Table 6. It is known from the examples that the hydrogen produced by the electrolyte solution is mild and the self-discharge of the sodium hydroxide series is also less than that of the potassium hydroxide series. In addition, the higher the indium content in the zinc powder, the better the result, and the smaller the amount of lead monoxide added. When the battery was actually trial-produced, the generated value was less than the amount of hydrogen gas generated in the experiment of Example 12. Because the copper sheet used in Example 12 is different from the actual collector structure, the generated hydrogen is partially consumed due to factors such as silver oxide reduction. The method of Example 12 has different hydrogen production, but it is sufficient as a method for observing the substitution characteristics used to predict the actual hydrogen production of batteries. The same experiment is also used for indium compounds, tin compounds containing tetravalent tin, and mixtures other than lead monoxide. If the result is substantially the same as lead monoxide, the paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling in this page). Binding-41-Central Standards of Ministry of Economic Affairs A7 B7 printed by the Bureau ’s Consumer Cooperative. V. Description of the invention (3g) It is found that the battery capacity is reduced. When adding zinc oxide powder of 5 0 0 p pm indium, 1 0 0-1 0 0 0 P pm inhibitor can be added, and In the case of adding 1 800 0 P pm indium zinc powder, you can add 1 〇 1 0 0 0 0 PP m inhibitor to inhibit. Example 1 5-1 7 illustrates the use of zinc containing no more than 4 p pm iron and one or more species selected from indium compounds, tin compounds containing tetravalent tin, and oxidized compounds as zinc inhibitors of the present invention Effect. &lt; Example 1 5 &gt; Zinc powder containing gallium produced by a 100 ppm spray method, 200 ppm indium, 500 ppm lead and 450 ppm silver, and additionally containing 5 ppm iron. The iron concentration in the zinc powder is adjusted by removing the magnet. The concentration after removing iron was confirmed by atomic absorption method. Hydrogen generation test is to add 2 g of zinc powder in advance to a special test tube with a volume of 2 to know the amount of gas generated, and a copper sheet with the area of 0 · 6 cm2 and a thickness of 0 · lmra that is the same as the collector material, and add the test electrolyte The solution was heated to 60 ° C, and the volume of hydrogen produced was measured for 7 days. Repeat the test 10 times, and take the average value as the result. The preparation method of the electrolyte solution is, if it is a potassium hydroxide system, add nearly saturated zinc oxide to the 30% potassium hydroxide solution, if it is a sodium hydroxide series, add it to the 25% sodium hydroxide solution Nearly saturated zinc oxide is used as a matrix, and lead monoxide and other substances are added as inhibitors. Table 7 shows the iron concentration in the zinc powder and the amount of hydrogen generated relative to the amount of inhibitor added. The amount of inhibitor added is relative to the p P m table size of the electrolyte solution. The paper size is applicable to the Chinese National Standard (CNS) Α4 specification (210X297 mm) (please read the precautions on the back and fill in this page) • Pack. Order A7 B7 V. Description of invention (40). The results of the hydrogen generation amount are also shown in Table 7. (Please read the precautions on the back and then fill out this page) 装 -s The paper standard printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 43-Central Standard of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 2 ⑽ 5 Ο 8 Α7 Β7 V. Description of the invention (41) Table 7 · Hydrogen rate test number produced by zinc powder Electrolyte content in electrolyte zinc powder ppm ppm Pb 0 in Australia electrolyte ppm hydrogen Release rate ML / g / day 1 K 0 Η 5 5 0 5 7 0. 0 0 2 Κ 0 Η 5 10 0 5 3.75 3 Κ 0 Η 5 5 0 0 5 6.25 4 Κ 0 Η 5 10 0 0 7 9.29 5 Κ 0 Η 5 5 0 0 0 12 0. 85 6 Κ 0 Η 5 0 15 8.92 7 Κ 0 Η 5 10 2 8 4.2 8 8 Κ 0 Η 4 5 0 5 0 8.9 4 Θ Κ 0 Η 4 10 0 2 1.14 10 Κ 0 Η 4 5 0 16.13 11 Κ 0 Η 4 10 0 2 0.15 12 Κ 0 Η 4 5 0 0 4 5.21 13 Κ 0 Η 4 10 0 0 5 0.56 14 Κ 0 Η 4 5 0 0 0 2 0 1.73 15 Κ 0 Η 2 0 5 16.92 16 Κ 0 Η 2 10 12.50 17 Κ 0 Η 2 5 0 12.50 18 Κ 0 Η 2 10 0 14.29 1 9 Κ 0 Η 2 5 0 0 3 0.21 2 0 Κ 0 Η 2 10 0 0 5 3.57 2 1 Κ 0 Η 2 5 0 0 0 16 2.85 2 2 Ν a 0 Η 5 0 4 2 3. 8 5 2 3 Ν a 0 Η 5 10 4 2.36 2 4 Ν a 0 Η 5 5 0 4 0.23 2 5 Ν a 0 Η 5 10 0 6 6.34 2 6 Ν a 0 Η 5 5 0 0 10 0.25 2 7 Ν a 0 Η 5 10 0 0 13 2.58 2 8 Ν a 0 Η 5 5 0 0 0 2 7 8.9 0 2 9 Ν a 0 Η 4 0 3 9 6.3 7 3 0 Ν a 0 Η 4 10 19.36 3 1 Ν a 0 Η 4 5 0 12.72 3 2 Ν a 0 Η 4 10 0 15.64 3 3 Ν a 0 Η 4 5 0 0 3 8.38 3 4 Ν a 0 Η 4 10 0 0 4 7.25 3 5 Ν a 0 Η 4 5 0 0 0 19 0. 01 3 6 Ν a 0 Η 2 0 4 3.56 3 7 Ν a 0 Η 2 10 11.23 3 8 Ν a 0 Η 2 5 0 10.12 3 9 Ν a 0 Η 2 10 0 12.93 4 0 Ν a 0 Η 2 5 0 0 2 7.81 4 1 Ν a 0 Η 2 10 0 0 4 2.21 4 2 Ν a 0 Η 2 5 0 0 0 13 0.10 -------- (installed- ----- Subscribe ------ {I (Please read the precautions on the back before filling in this page) This paper size is applicable to China National Standard (CNS) A4 specification (210X 297mm) -44-Ministry of Economic Affairs A7 B7 printed by the Central Consumer Service Cooperative Employees V. Description of Invention (42) The results of hydrogen generation in the electrolyte solution of the potassium hydroxide series are shown in Figure 8. Figure 1 is the case of using zinc powder containing 5 p pm iron, which usually produces more hydrogen than the other two. 2 is the case of using zinc powder containing 4 p pm iron, and the addition of lead monoxide is not less than 10 P pm has the effect of suppressing the generation of hydrogen. 3 is the case of using zinc powder containing 2 p pm iron, and the concentration range is the same as when 2 "especially when the iron impurity is not more than 4 p pm, the effect of adding lead monoxide is not more than 1 0 0 P pm Obviously, it can reduce the amount of environmental pollutant lead. In this example, the iron was removed by magnetite to reduce the iron concentration. However, it can also be used in the zinc powder production step to purify iron-removed zinc as the zinc powder, and obtain substantially the same results. &lt; Example 16 &gt; A part of the electrolyte solution and 116 mg were added to the anode can in the anode can, and the pellets (silver oxide content 98%) were added to the silver oxide, and the polyethylene separator and Cellophane separator. Next, push the nylon pad into the anode tank, add penetrant, gelling agent, 30 zinc powder, inhibitor, etc., add the remaining electrolyte solution drop by drop, and place the cathode seal to produce 100 various button types Silver oxide battery. The size of the battery produced is the same as S R 6 2 1 type. Then, an electrolyte solution was prepared so that the amount of lead monoxide added was an amount relative to the amount of zinc. After storing at 60 ° C for 20 days (reportedly equivalent to 1 year at room temperature), the self-discharge rate was measured. The results are shown in Table 8. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 public daughter 1 (please read the precautions on the back and then fill out this page). Binding -45-, ^ A7B7 Printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Description of the invention (43) Table 8 • Battery self-discharge rate and hydrogen release rate experiment number Electrolyte zinc powder Ning indium contains child ppm Pb 0 in the electrolyte degree of collapse ppm self-releasing rate% hydrogen release rate KL / g / day 1 K 0 Η 5 0 13.2 0.98 2 Κ 0 Η 5 10 8. 7 0.76 3 Κ 0 Η 5 5 0 7. 2 0.79 4 Κ 0 Η 5 1 0 0 4. 0 0.48 5 Κ 0 Η 5 5 0 0 8. 6 0.64 6 Κ 0 Η 5 10 0 0 8. 5 0.77 7 Κ 0 Η 5 5 0 0 0 16.2 1.48 8 Κ 0 Η 4 0 13.0 0.89 9 Κ 0 Η 4 10 3. 8 0.45 10 Κ 0 Η 4 5 0 3. 5 0.37 11 Κ 0 Η 4 10 0 2. 2 0.33 12 Κ 0 Η 4 5 0 0 2. 8 0.29 13 Κ 0 Η 4 10 0 0 3. 9 0.40 14 Κ 0 Η 4 5 0 0 0 17.6 1.42 15 Κ 0 Η 2 0 11.0 0.82 16 Κ 0 Η 2 10 2. 2 0.24 17 Κ 0 Η 2 5 0 1.5 .3 0.23 18 Κ 0 Η 2 10 0 1. .4 0.21 19 Κ 0 Η 2 5 0 0 2. 2 0.25 2 0 Κ 0 Η 2 10 0 0 3. 5 0.33 2 1 Κ 0 Η 2 5 0 0 0 17.2 1.62 2 2 Ν a 0 Η 5 0 10.1 0.92 2 3 Ν a 0 Η 5 10 8. 0 0.72 2 4 Ν a 0 Η 5 5 0 5. 5 0.67 2 5 Ν a 0 Η 5 10 0 4. 1 0.40 2 6 Ν a 0 Η 5 5 0 0 7. 4 0.65 2 7 Ν a 0 Η 5 10 0 0 7. 2 0.73 2 8 Ν a 0 Η 5 5 0 0 0 14.2 1.28 2 9 Ν a 0 Η 4 0 9. 2 0.80 3 0 Ν a 0 Η 4 10 3. 7 0.35 3 1 Ν a 0 Η 4 5 0 2. 0 0.29 3 2 Ν a 0 Η 4 10 0 2. 0 0.29 3 3 Ν a 0 Η 4 5 0 0 2. 2 0.26 3 4 Ν a 0 Η 4 10 0 0 3. 2 0.41 3 5 Ν a 0 Η 4 5 0 0 0 15.2 1.31 3 6 Ν a 0 Η 2 0 7. 1 0.72 3 7 Ν a 0 Η 2 10 1. 5 0.25 3 8 Ν a 0 Η 2 5 0 0. 8 0.19 3 9 Ν a 0 Η 2 10 0 0. 7 0.18 4 0 Ν a 0 Η 2 5 0 0 1 . 1 0.23 4 1 Ν a 0 Η 2 10 0 0 2. 9 0.28 4 2 Ν a 0 Η 2 5 0 0 0 9. 8 1.46 {Binding ^ ^ (please read the precautions on the back before filling this page) this The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) I 46-A7 B7 printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy V. Description of the invention (44) The results show that the iron content is not more than 4 p pm of When the powder is added in the battery 1 0_ 1 0 0 P pm - lead oxide to suppress the self-discharge rate of not more than 4%. The reason why the addition of high concentration of lead monoxide reduces the battery capacity is that needle-shaped crystals of lead are generated when excessively added, so it may cause a short circuit. &lt; Example 1 7 &gt; Using the method of Example 16 a button-type silver oxide battery using a polypropylene liner permeable to hydrogen was prepared. Place 10 silver oxide batteries prepared in a high-temperature bath in a glass container filled with liquid paraffin, attach a graduated collecting tube at the top, and measure the amount of hydrogen produced. This state is maintained at 60 ° C for 20 days (it is said to be approximately equivalent to one year), and the amount of hydrogen generated after 20 days is evaluated. The results are shown in Table 8. It is known from the examples that the hydrogen produced by the electrolyte solution is mild and the self-discharge of the sodium hydroxide series is also less than that of the potassium hydroxide series. In addition, the higher the indium content in the zinc powder, the better the result, and the smaller the amount of lead monoxide added. When the battery was actually trial-produced, the generated value was less than the amount of hydrogen gas generated in the experiment of Example 15. Because the copper sheet used in Example 15 is different from the actual collector structure, the generated hydrogen is partially consumed by the reduction of silver oxide and other factors. The method of Example 15 differs in the amount of hydrogen produced, but it is sufficient as a method for observing the substitution characteristics used to predict the actual amount of hydrogen produced by the battery. The same experiment is also used for indium compounds, tin compounds containing tetravalent tin, and mixtures other than lead monoxide. The results are essentially the same as those of lead monoxide. It has been found that the battery capacity has been reduced. Add 10-1 0 0 〇p pm inhibitor. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the back (Please fill in this page again)

、 1T -47-A 7 B7 V. Description of the invention (45) ‘It can suppress the self-discharge rate not more than 4%. The present invention has described iron which is the most likely pollutant and has the highest risk of hydrogen generation. However, it is preferable to reduce impurities such as nickel, cobalt, and antimony as much as possible. In addition, in the case of a cathode active material with a large amount of hydrogen generation, such as zinc, it is difficult to form a uniform film due to a hydrogen generation reaction on the surface that competes with lead deposition, so the effect of lead deposition becomes small. Therefore, the use of cathode active materials in which zinc is added with indium, bismuth, lead, aluminum, gallium, calcium, etc. can suppress the generation of hydrogen gas to some extent. Example 1 8-2 1 illustrates the effect of controlling battery humidity. &lt; Example 18 &gt; A part of the electrolyte solution and 116 mg were added to the anode can, and the pellets (silver oxide content 98%) were added to the silver oxide, and the polyethylene separator and Cellophane separator. Secondly, push the nylon pad into the anode can, add penetrant, gelling agent '30 mg zinc powder, inhibitors, etc., add the remaining electrolyte solution drop by drop, and place the cathode seal to produce a button-type silver oxide battery. " Printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page). For the electrolyte preparation method, if it is a potassium hydroxide series, add a solution close to saturation in a 30% potassium hydroxide solution. For zinc oxide, if it is a sodium hydroxide system, add nearly saturated zinc oxide 'as a matrix to the 25% sodium hydroxide solution, and optionally add inhibitors. When the inhibitor is added, it weighs 1000 ppm with respect to zinc and dissolves in the electrolyte solution. Place 10 coin-shaped or button-shaped silver oxide batteries in a glass container filled with liquid paraffin in a high-temperature bath, and attach the paper with scales at the top to the Chinese National Standard (CNS) A4 (210X297 %) I 48-A7 ___B7 V. Description of the invention (46) Collection tube, measure the amount of hydrogen produced. In this case, maintain the temperature at 60 ° C for 20 days (it is said to be equivalent to about 1 year), and evaluate the amount of generated hydrogen gas and the self-discharge rate after 20 days. Connect and discharge a 2 5 Ω resistor to measure the battery capacity. The self-discharge rate was calculated from the battery capacity change of the same battery stored at 60 ° C for about 20 days. The size of the coin-shaped or button-shaped silver oxide battery produced and evaluated, the metal content in the zinc powder used, the electrolyte solution, the humidity, the added inhibitor, and the amount of hydrogen generated after storage at 60 ° C for 20 days and self-discharge The rates are shown in Table 9 and Table 10. (Please read the precautions on the back before filling out this page) Install _, set the size of the paper printed by the Beigong Consumer Cooperative of the Central Bureau of Prototyping of the Ministry of Economic Affairs. The paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -49-B7 V. Description of the invention (47) Printed by the Employees ’Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 9. The hydrogen release rate and self-discharge rate of the battery The experiment of the pond surface quality at lmg fragmentation inhibition rate is stored at 60 ° C for 20 days in the room Aging rate number (ppm vs. fresh) The amount of water added in the hydrogen release rate White body discharge rate White body discharge rate White body discharge rate Ga In Pb B i A 1 ML / g / day% ^ L / g / day% 1 SR626 500 500 500 NaOH 0.448-0.37 3.00 0.00 3.10 2 SR626 500 500 500 KOH 0.428-0.39 2.50 0.00 2.50 3 SR626 500 500 NaOH 0.448 — 0.41 2. 70 0.00 2.60 4 SR626 500 500 KOH 0.428 — 0.47 2.40 0.00 2. 50 5 SR626 100 200 500 450 NaOH 0.448 — 0.40 2.50 0.00 2.60 6 SR626 100 200 500 450 KOH 0.428-0.46 2.60 0.00 2.60 7 SR621 500 500 500 NaOH 0.459 — 0.38 2.10 0.00 2.10 8 SR621 500 500 500 KOH 0.4 40 — 0.40 3.10 0.00 3.30 9 SR621 500 500 NaOH 0.459-0.43 2.80 0.00 2. 70 10 SR621 500 500 KOH 0.440-0.45 2.70 0.00 2.70 11 SR516 500 500 500 NaOH 0.476-0.35 2.80 0.00 2.70 12 SR516 500 500 500 KOH 0.455 — 0.37 2.80 0.00 2.60 13 SR516 500 500 NaOH 0.476-0.41 2.90 0.00 2.50 14 SR516 500 500 KOH 0.455 — 0.45 3.00 0.00 2.90 15 SR527 500 500 500 NaOH 0.488-0.38 2. 70 0.00 2.80 16 SR527 500 500 500 KOH 0.463-0.39 2.60 0.00 2.60 17 SR527 500 500 NaOH 0.488-0.43 2.50 0.00 2.40 18 SR527 500 500 KOH 0.463-0.47 2. 70 0.00 2.60 19 SR726 500 500 500 NaOH 0.441-0.35 2.10 0.00 2.50 (Please read the notes on the back before filling this page ) The size of the bound and printed paper is in accordance with the Chinese National Standard (CNS) A4 specification (2 丨 0 '297 mm) 50 Printed by the employee consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A7 _B7 V. Description of invention (48) Table 10. Battery's gas stalk output rate and self-discharge rate experimental battery view / Year edition 猇 (ppm vs crude) Water added hydrogen stroke rate White body discharge rate White body discharge rate Ga In Pb B i A 1 ^ L / g / day% ML / g / day% 20 SR726 500 500 500 KOH 0.423-0.36 1.50 0.00 2.00 21 SR726 500 500 NaOH 0.441 — 0.37 1.90 0.00 1.80 22 SR726 500 500 KOH 0.423-0.45 2.20 0. 00 2.10 23 SR1120 500 500 500 NaOH 0.441-0.35 1.90 0.00 2.10 24 SR1120 500 500 500 KOH 0.423 -0.34 2.60 0.00 2.10 25 SR1120 500 500 NaOH 0.441-0.37 2.30 0.00 2.20 26 SR1120 500 500 KOH 0. 423-0.38 2. 40 0. 00 2.50 27 SR626 500 500 500 NaOH 0.448 Sulfur surface 0.33 2.50 0.00 2,50 28 SR626 500 500 500 KOH 0.428 Sulphur surface 0.35 2.30 0.00 2.60 29 SR626 500 500 NaOH 0.48 Sulphur 0.38 2.70 0.00 2.50 30 SR626 500 500 KOH 0.428 mm 0.42 2,80 0.00 2. 90 31 SR626 100 200 500 450 NaOH 0.448 Sulphur surface 0. 37 2.70 0.00 2. 70 32 SR826 100 200 500 450 KOH 0.428 sulfur_ 0.41 2.80 0.00 2.80 33 SR626 500 NaOH 0.448 sulfur surface 0.39 2.80 0.00 2.70 34 SR626 500 KOH 0.428 Sulphur surface 0.42 2.60 0.00 2.60 35 SR626 500 NaOH 0.448 Amino lion surface 0.42 2. 70 0.00 2.50 36 SR626 500 KOH 0.428 Amino surface 0. 45 2.70 0.00 2.40 37 SR626 500 NaOH 0.448 PbO 0.42 2. 50 0. 00 2 . 90 38 SR626 500 KOH 0.428 PbO 0. 44 2.50 0.00 2. 20 (please read the precautions on the back before filling in this page). Packing. The size of this paper is applicable to China National Standard (CNS) A4 specification (210X297mm)- 51-V. Description of the Invention (49) In Tables 9 and 10, the weight of zinc is expressed in p pm relative to the added metal composition. Humidity is expressed in mg of water per 1 mg of zinc. The unit of hydrogen production is / z / g / day. In the right column of the table, the daily hydrogen production relative to the zinc production is listed at 60 ° C for 20 days and at room temperature for one year. The unit of rate is%. I η — sulfate is indium sulfate, I η_ aminosulfonate is indium aminosulfonate, and PbO is lead oxide. When the amount of hydrogen gas is converted to normal temperature value, all values are suppressed to no more than 0.03 #j? / g / day. In addition, the self-discharge rate can be no more than 4% / year. &lt; Example 1 9 &gt; In order to confirm whether the storage at 60 ° C for 20 days in Example 18 is indeed equivalent to one year at normal temperature, the actual test is one year. The gasket used in Example 18 was replaced with a nylon made in the production of general silver oxide batteries, and coin-shaped or button-shaped silver oxide batteries were produced in the same way. Printed by the Beigong Consumer Cooperative of the Central Bureau of Economic Affairs of the Ministry of Economic Affairs (please read the precautions on the back before filling out this page) 10 silver oxide batteries made in a liquid paraffin filled in a high temperature bath at 25 ° C In the glass container, a collection tube for generating hydrogen is attached to the top. This condition is maintained for 1 year, and the hydrogen generation amount and self-discharge rate are evaluated after 1 year. The measurement method is the same as in Example 18. The results of hydrogen generation and self-discharge rate are shown on the right side of Table 9 and Table 10. Test results, all samples did not generate gas. This is because the trace hydrogen produced in the battery is consumed by the reduction of silver oxide. The self-discharge rate is substantially the same as that maintained at 60 ° C for 20 days, and all values are not greater than 4%. This paper scale is applicable to China National Standard (CNS) A4 specification (210X 297mm) -52-A7 B7 printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (5〇) &lt; Example 2 0 &gt; If the electrolyte solution is a potassium hydroxide system, use zinc oxide in potassium hydroxide to near saturation. The amount of electrolyte solution to be added per 1 mg of zinc is 0. 37 to 0.96 mg, which is 0.25 to 0.65 1 ^ when converted to water. It is the same as in Example 18, using zinc containing 111 indium, bismuth and bismuth in each 500 ports And polypropylene liner, silver oxide battery with SR 6 2 6 size was prepared, and storage test was carried out at 60 ° C for 20 days. The amount of generated hydrogen gas relative to the amount of added water is shown in Fig. 9. The amount of hydrogen produced is produced daily by lg zinc in units of / zj / g / day. According to this result, it is known that when the amount of water is not less than 0.3 lmg, the amount of hydrogen generation is reduced to not more than 0.54 / zi? / G / day (converted to a normal temperature value of 0.03vi? / G / day). In addition, when the amount of water was not less than 0.57 mg, liquid leakage was found. In the same way, using the electrolyte solution of the sodium hydroxide system, the amount of electrolyte solution added per 1 mg of zinc changes from 0.3 6 to 0.9 2 mg (calculated as the amount of water from 0. 25 to 0.65 mg), at 60 Store at 20 ° C for 20 days. Results τκ in Figure 10. It is known that when the amount of water is not less than 0.32 mg, the amount of generated hydrogen is reduced to not more than 0.54; ae / g / day. In addition, when the amount of water becomes not less than 0.59 mg, liquid leakage occurs. That is, when the electrolyte solution is a potassium hydroxide system, the amount of water added per 1 zinc is 0.3 1 — 0. 57mg 'and if it is sodium hydroxide it is 0.32-0.59 mg. This paper scale is applicable to the Chinese National Standard (CNS) A4 (210X 297mm) (please read the precautions on the back before filling in this page) Binding · Order-53-A7 printed by Beigong Consumer Cooperatives, Central Bureau of Economics and Trade, Ministry of Economic Affairs B7 V. Description of the invention (51) &lt; Example 2 1 &gt; To confirm whether the amount of hydrogen generated in the water range of Example 20 is not greater than 0.554ee / g / day and the liquid is not leaking, take Example 19 Methods The room temperature storage test was conducted for 1 year and tested. In the case of a potassium hydroxide system, the amount of electrolyte solution added is such that the amount of added water in 1 mg of zinc becomes 0.31, 0.44 and 0.57 mg. In the same way, if it is a sodium hydroxide system, the amount of electrolyte solution added is such that the amount of water becomes 0.32, 0.45 and 0 · 59 mg. As in Example 20, the gasket was replaced with nylon, and 10 silver oxide batteries were individually produced. According to the test results of the silver oxide battery manufactured at room temperature for 1 year, no hydrogen is generated, and the self-discharge rate is not more than 4%, and no practical problems have been found. According to Examples 22-24, the effect of combining each technology will be described. Before actually evaluating the battery characteristics, a special test tube is used to evaluate the amount of hydrogen generated by each inhibitor and the plated copper plate. The method used is described below. In a special test tube with a volume of 25 m 5 and a scale to recognize the amount of gas produced, 2 g of zinc powder containing bismuth, indium and lead prepared by a spray method of 500 p pm each, and an area of 0. A copper sheet of 6 cm2 and a thickness of 0.1 mm (the material is the same as the collector), add the electrolyte solution used for the test and heat to 60 ° C, and measure the volume of hydrogen produced over 7 days. The test was repeated 10 times and the result was the average value. The preparation method of electrolyte solution is, if it is potassium hydroxide series, then add nearly saturated zinc oxide in 30% potassium hydroxide solution. If it is sodium hydroxide series, add it in 25% sodium hydroxide solution. Nearly saturated zinc oxide is used as a matrix and inhibitors are added at will. This paper scale is applicable to the Chinese National Standard (CNS) A4 (210X297mm) (please read the precautions on the back before filling out this page) Binding · Order -54-Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A 7 B7 Five 2. Description of the invention (52) &lt; Example 3 2 &gt; At the same time, a copper plate subjected to electroplating and substitution electroplating and an inhibitor were used to measure the hydrogen produced by zinc. The plating process is as follows. * Indium (I η) electroplating

Method: Electroplating Plating bath: 2 5 ° C: Indium sulfate 60g / i ?: Sodium sulfate 10 g / thickness: 0.3em * Tin (S η) electroplating

Method: Electroplating bath: 70 ° C: potassium stannate 100g / i2: potassium hydroxide 15 g / i ?: potassium acetate 5 g / i? Coating thickness: 0.3 / zm * zinc indium (Zn—In ) Plating method: contact plating (copper plate and zinc are placed in a plating bath heated to below 60 ° C and left for 1 hour) Plating bath: KOH 30%: Z η Ο Saturation: Indium sulfate 0.3% Coating thickness: 0.3em in The results of the electro-ammonium compound on the copper plate and the generation of hydrogen relative to the inhibitor indicate that the paper size is applicable to the Chinese National Standard (CNS) Μ specification (210X 297mm) (please read the precautions on the back before filling this page) -a -55-A7 B7 Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy ^ 9508 V. Invention description (53) is shown in Table 11 (using KOH series) and Table 12 (using NaOH series). (Please read the precautions on the back before filling this page) This paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) -56-A7 B7 5. Invention description (54) Table 1 1 Hydrogen release rate of copper plate Printed by the Ministry of Economy Central Standards Bureau Staff Consumer Cooperative Experiment Number Electrolytic Inhibitor (Concentration: 100ppm) Hydrogen Generation Rate KL / g / day 1 In KOH — 3 1.43 2 In KOH Indium Sulphate 14. 28 3 In KOH indium sulfamate 12.41 4 In KOH indium hydroxide 16.73 5 In KOH lead oxide 17.85 6 In KOH barium hydroxide 8.57 7 In KOH carbon fluoride 12.14 8 Sn KOH — 35. 78 9 Sn KOH indium sulfate 16.11 10 Sn KOH indium sulfamate 17.72 11 Sn KOH indium hydroxide 16.53 12 Sn KOH lead oxide 17.91 13 Sn KOH barium hydroxide 10.89 14 Sn KOH carbon fluoride 14.38 15 Zn * In KOH — 32. 34 16 Zn * In KOH sulfuric acid Indium 15.27 17 Zn * In KOH indium sulfamate 13.35 18 Zn * In KOH indium hydroxide 18.83 19 Zn · In KOH lead oxide 16.82 20 Zn · In KOH barium hydroxide 11.30 21 Zn * In KOH fluorocarbon 13.01 This paper Scale applies to Chinese countries Associate (CNS) A4 size (2 Shu 0X297 mm) (Please read the back of the precautions to fill out this page) installed., Ιτ A7

7 B V. Description of invention (55) Table 1 2 · Hydrogen release rate of electroplated copper plate Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy Experiment number Electrolytic inhibitor (concentration: 100ppm) Hydrogen release rate ML / g / Day 22 In NaOH — 29.41 23 In NaOH indium sulfate 14.75 24 In NaOH indium sulfamate 10.58 25 In NaOH indium hydroxide 15.37 26 In NaOH lead oxide 14.14 27 In NaOH barium hydroxide 7. 82 28 In NaOH fluorine Carbonization · P0E 9.34 29 Sn NaOH — 30.10 30 Sn NaOH Indium sulfate 15.03 31 Sn NaOH Indium sulfamate 15.28 32 Sn NaOH Indium hydroxide 15.38 33 Sn NaOH Lead oxide 14.53 34 Sn NaOH Barium hydroxide 8.72 35 Sn NaOH Carbon fluoride · P 0 E 12.43 36 Zn · In NaOH — 32.83 37 Zn * In NaOH indium sulfate 14.98 38 Zn * In NaOH indium sulfamate 13.19 39 Zn * I n NaOH indium hydroxide 14.13 40 Zn · In NaOH oxidation Lead 14.27 41 Zn · In NaOH Barium Hydroxide 9.98 42 Zn · In NaOH Carbon Fluoride · P 0 E 9.84 The paper size is applicable to China National Standard (CNS) A4 specification (210X 297mm) (please read the back Matters needing attention Page), \-° -58-A7 B7 V. Description of the invention (56) The concentration of the inhibitor is expressed in terms of the value relative to the electrolyte solution. As for the fluorocarbon (fluorocarbon) -polyoxyethylene (POE) series of surfactants, the one with a fluorocarbon carbon number of 10 and a POE polymerization degree of 50 is used. In general, if the carbon number of the fluorocarbon is 4_2 0 and the POE polymerization degree is 3-1 0 0, the same effect can be obtained. Compared with those who do not add an inhibitor, the addition of the inhibitor of the present invention reduces the amount of hydrogen generated to about 1/3 to 1/2, so the effect of suppressing the generation of hydrogen is known. The difference due to plating or inhibitors is not significant. In addition, the amount of hydrogen gas generated relative to the test date is shown in Fig. 11 using the measurement results of indium-plated copper plates. Among indium compounds, only indium sulfate is shown in the figure. In this example, the results obtained using a plating thickness of 0.3 are shown. However, in practice, the results with a thickness of 0.3 have very little difference. &lt; Comparative Example 3 &gt; For comparison, the experiment was carried out using the electroless copper plate according to the method of Example 22. The experimental results are shown in Table 13 and FIG. 12. (Please read the precautions on the back before filling this page) 4β

T The Ministry of Economic Affairs, Central Standards Bureau, Employee Consumer Cooperative printed this paper using the Chinese National Standard (CNS) A4 specification (210X297 mm) -59-A7 B7 V. Description of invention (57) Table 1 3 · Unplated copper plate Hydrogen release rate Printed example of an electrolyte inhibitor (concentration: 1 0 0 ρ ρ m) printed by the Employee Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Hydrogen generation rate KL / g / 1 Κ 0 Η — 5 16. 00 2 Κ 0 Η sulfuric acid Indium 3 0.56 3 Κ 0 Η Indium sulfamate 2 8.73 4 Κ 0 Η Indium hydroxide 2 9.07 5 Κ 0 Η Lead oxide 2 4.15 6 Κ 0 Η Barium hydroxide 480.32 7 Κ 0 Η Fluorocarbon · P 0 E 465.29 8 Ν a 0 Η — 450. 24 9 Ν a 0 Η indium sulfate 2 5.86 10 Ν a 0 Η indium sulfamate 2 7.59 11 Ν a 0 Η indium hydroxide 2 5.48 12 Ν a 0 Η lead oxide 2 0.25 13 Ν a 0 Η barium hydroxide 400. 44 14 Ν a 0 Η vaporized carbon · P 0 E 392.91 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back first Please fill out this page again) 装 _, ιτ A7 B7 V. Description of invention (58) It is known that no inhibitor is added and hydrogen hydroxide is added When fluorocarbon or a series of polymerization of ethylene oxide surfactant, the amount of hydrogen gas generated as the number of days refers to the number of trials increases. On the other hand, it is known that the addition of indium sulfate and lead oxide suppresses the generation of hydrogen gas. This is because indium or lead compounds have the function of coating copper plates, but barium hydroxide and surfactants do not. &lt; Example 23 &gt; A copper plate plated in the manner of Example 22 was used, and the amount of hydrogen gas generated by combining the inhibitors was measured using a KOH series electrolyte solution. The results are shown in Table i 4 (please read the precautions on the back and then fill out this page). Binding and ordering. This paper is printed by the Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The paper standard is applicable to the Chinese National Standard (CNS> A4 specification (210X297 mm) -61 V. Description of the invention (59) Table 14. Hydrogen release rate using indium-plated copper plate and inhibitor Inhibitor concentration printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperatives PP m Hydrogen generation rate number Indium lead oxide hydrogen sulfate Barium Oxide Carbon FluoridePOE PL / g / day 43 100 100 0 0 15. 82 44 100 0 100 0 10.10 45 100 0 0 100 13.41 46 0 100 100 0 14. 64 47 0 100 0 100 15. 54 48 0 0 100 100 12.47 49 100 100 100 0 14. 87 50 100 100 0 100 12.21 51 100 0 100 100 13.05 52 100 100 100 100 13.94 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please first Read the precautions on the back and then fill out this page) ·-* Xu- it '-3

I i- -62-A7 B7 5. Description of the invention (60) The inhibitor column in the table shows the concentration of inhibitor added relative to the electrolyte solution. It is known that the amount of generated hydrogen gas is extremely low as in the example, and even if various inhibitors are used, the effect is not too bad. Secondly, the battery is actually produced, and the plating effect and inhibitor effect on the collector are evaluated. &lt; Example 2 4 &gt; A part of the electrolyte solution and 1 16 rag were added to the anode can to add the combination agent to the tablets molded in silver oxide (silver oxide content 98%), and a polyethylene separator and Cellophane separator. Secondly, push the nylon pad into the anode tank, add penetrant, gelling agent, 30 mg zinc powder, inhibitor, etc., add the rest of the electrolyte solution with inhibitor added drop by drop, and place the cathode seal to produce 1 0 0 various button-type silver oxide batteries. The types and thickness of the plating on the cathode can, the type and concentration of the added inhibitor, the closed circuit voltage and the self-discharge rate are shown in Tables 15 and 16. (Please read the precautions on the back before filling in this page). Packing. This paper is printed by the Beigong Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs. The paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210'〆297mm) -63- 5. Description of the invention (61) A7 B7 Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 15. Battery characteristics with K〇Η electrolyte test number electrolyte type inhibitor concentration ppm white body discharge rate% closed circuit voltage V indium sulfate hydrogen oxide Barium Oxide Carbon Fluoride • POE Partially Discharged New Battery Battery Newly Discharged Battery 53 — 0 0 0 0 5.6 9.4 1.159 1.180 54 In 0 0 0 0 4.5 6.2 1.165 1.192 55 In 1000 0 0 0 2.6 2.7 1.169 1.198 56 In 0 1000 0 0 2.7 2.8 1.168 1.197 57 In 0 0 1000 0 2.5 4.9 1.185 1.198 58 In 0 0 0 1000 2.9 5.1 1.165 1.185 59 In 1000 1000 0 0 2.5 2.6 1.168 1.198 60 In 1000 0 1000 0 2.4 2.6 1.185 1.239 61 In 1000 0 0 1000 2.5 2.7 1.168 1.198 62 In 0 1000 0 1000 2.6 2.7 1.167 1.197 63 In 0 1000 1000 0 2.7 2.7 1.167 1.238 64 In 0 1000 1000 1000 2.6 2.6 1.186 1.2 38 65 In 1000 1000 1000 0 2.6 2.7 1.186 1.129 66 In 1000 1000 0 1000 2.7 2.7 1.168 1.198 67 In 1000 0 1000 1000 2.6 2.6 1.185 1.238 68 In 1000 1000 1000 1000 2.6 2.7 1.185 1.238 69 Sn 0 0 0 0 5.7 10.5 1.160 1.181 70 Sn 1000 0 0 0 4.7 6.8 1.166 1.193 71 Sn 0 1000 0 0 2.7 2.7 1.171 1.198 72 Sn 0 0 1000 0 2.7 2.8 1.170 1.198 73 Sn 0 0 0 1000 2.6 5.0 1.186 1.197 74 Sn 1000 1000 0 0 3.0 5.3 1.165 1.187 75 Sn 1000 0 1000 0 2.6 2.7 1.169 1.199 {install ------ order ------ ί W (please read the precautions on the back first and then fill out this page) This paper scale is applicable to China National Standards (CNS ) Α4 specification (210X 297 mm) 64-A7 B7 printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of invention (62) Table 1 5 (continued) Experimental editor electrolyte type inhibitor concentration ppm white body discharge rate% closed circuit Voltage V Indium Sulfate Lead Oxide Barium Hydroxide Carbon Fluoride • POE New Battery Partially Discharged New Battery Partially Discharged Battery 76 Sn 1000 0 0 1000 2.4 2.5 1.187 1.240 77 Sn 0 1000 0 1000 2.4 2.8 1.169 1.200 78Sn 0 1000 1000 0 2.5 2.6 1.168 1.197 79 Sn 0 1000 1000 1000 2.7 2.8 1.169 1.240 80 Sn 1000 0 1000 0 2.5 2.8 1.188 1.240 81 Sn 1000 1000 0 1000 2.8 2.8 1.186 1.131 82 Sn 1000 0 1000 1000 2.8 2.8 1.170 1.199 83 Sn 1000 1000 1000 1000 2.7 2.6 1.186 1.239 84 Zn · In 0 0 0 0 5.7 9.8 1.166 1.193 85 Zn · In 1000 0 0 0 4.9 7.1 1.170 1.199 86 Zn · In 0 1000 0 0 2.8 2.7 1.170 1.197 87 Zn 0 1000 0 2.9 2.9 1.187 1.199 88 ZnIn In 0 0 0 1000 2.6 4.8 1.166 1.184 89 ZnIn 1000 1000 0 0 2.9 5.3 1.168 1.200 90 ZnIn 1000 0 1000 0 2.6 2.7 1.186 1.240 91 ZnIn 1000 0 0 1000 2.6 2.7 1.170 1.199 92 ZnIn 0 1000 0 1000 2.6 2.9 1.168 1.199 93 ZnIn In 0 1000 1000 0 2.7 2.7 1.168 1.238 94 ZnIn 0 1000 1000 1000 2.9 2.9 1.188 1.240 95 ZnIn 1000 1000 1000 0 2.8 2.8 1.188 1.131 96 Zn. In 1000 1000 0 1000 2.6 2.9 1.168 1.200 97 Zn · In 1000 0 1000 1000 2.9 2.8 1.187 1.239 98 Zn · In 1000 1000 1000 1000 2.7 2.7 1.186 1.239 (Please read the precautions on the back first (Write this page) Binding-, vs. Standard paper size is in accordance with Chinese National Standard (CNS) A4 specification (210X297mm) -65-A7 B7 V. Description of invention (63) Printed by the Consumers Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs 16 · Battery characteristics using N a Ο Η electrolyte Experiment number Electric MS Inhibitor concentration P pm White body discharge rate% Closed circuit voltage V Indium sulfate lead oxide barium hydroxide carbon fluoride • POE New battery partially discharged New battery partially discharged After the battery 99 — 0 0 0 0 5.3 9.0 1.158 1.180 100 In 0 0 0 0 4.2 5.9 1.164 1.193 101 In 1000 0 0 0 2.2 2.2 1.169 1.199 102 In 0 1000 0 0 2.2 2.4 1.167 1.197 103 In 0 0 1000 0 2.2 4.6 1.187 1.199 104 In 0 0 0 1000 2.5 4.8 1.166 1.186 105 In 1000 1000 0 0 2.1 2.3 1.169 1.199 106 In 1000 0 1000 0 1.9 2.2 1.186 1.239 107 In 1000 0 0 1000 2.0 2.5 1.169 1.197 108 In 0 1000 0 1000 2.3 2.6 1.169 1.196 109 In 0 1000 1000 0 2.3 2.2 1.169 1.238 110 In 0 1000 1000 1000 2.0 2.1 1.187 1.237 111 In 1000 1000 1000 0 2.4 2.4 1.186 1.131 112 In 1000 1000 0 1000 2.4 2.3 1.170 1.198 113 In 1000 0 1000 1000 2.3 2.0 1.187 1.239 114 In 1000 1000 1000 1000 2.2 2.5 1.186 1.237 115 Sn 0 0 0 0 5.5 10.2 1.160 1.183 116 Sn 1000 0 0 0 4.4 6.5 1.167 1.194 117 Sn 0 1000 0 0 2.4 2.3 1.173 1.199 118 Sn 0 0 1000 0 2.5 2.6 1.171 1.200 119 Sn 0 0 0 1000 2.4 4.7 1.186 1.197 120 Sn 1000 1000 0 0 2.7 5.0 1.166 1.186 121 Sn 1000 0 1000 0 2.2 2.5 1.170 1.201 (Please read the notes on the back first (Fill in this page again)

* tT The size of this paper is applicable to China National Standard (CNS) Α4 specification (210Χ297mm) 〇〇 CU 5 9 C5 9>

7 B Printed by the Consumer Labor Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (64) Table 1 6 (continued) Experiment number Plating type inhibitor concentration ppm White body discharge rate% Closed circuit voltage V Indium sulfate lead oxide barium hydroxide fluoride Carbon • POE New battery partially discharged battery New battery partially discharged battery 122 Sn 1000 0 0 1000 2.1 2.3 1.187 1.241 123 Sn 0 1000 0 1000 2.2 2.5 1.170 1.201 124 Sn 0 1000 1000 0 2.2 2.2 1.167 1.198 125 Sn 0 1000 1000 1000 2.2 2.5 1.171 1.241 126 Sn 1000 1000 1000 0 2.3 2.6 1.189 1.242 127 Sn 1000 1000 0 1000 2.6 2.5 1.187 1.133 128 Sn 1000 0 1000 1000 2.6 2.3 1.172 1.200 129 Sn 1000 1000 1000 1000 2.4 2.4 1.186 1.239 130 Zn · In 0 0 0 0 5.3 9.5 1.168 1.194 131 Zn * In 1000 0 0 0 0 4.6 6.6 1.171 1.201 132 Zn · In 0 1000 0 0 2.4 2.5 1.172 1.198 133 Zn · In 0 0 1000 0 2.5 2.7 1.187 1.200 134 Zn · In 0 0 0 1000 2.3 4.6 1.168 1.185 135 Zn · In 1000 1000 0 0 2.6 5.0 1.170 1.200 136 Zn · In 1000 0 1000 0 2.3 2.3 1.188 1.241 137 Zn · In 1000 0 0 1000 2. 2 2.4 1.171 1.198 138 Zn In 0 1000 0 1000 2.4 2.5 1.169 1.199 139 Zn In 0 1000 1000 0 2.6 2.5 1.167 1.237 140 Zn In 0 1000 1000 1000 2.7 2.6 1.187 1.242 141 Zn In 1000 1000 1000 0 2.4 2.3 1.188 1.132 142 Zn In 1000 1000 0 1000 2.6 2.7 1.167 1.201 143 Zn In 1000 0 1000 1000 2.6 2.6 1.189 1.240 144 Zn · In 1000 1000 1000 1000 2.5 2.5 1.186 1.240 (please read the precautions on the back before filling this page) This paper size is applicable to China National Standard (CNS) A4 Specification (210X297mm) -67-A7 B7 Printed by the Employee Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs V. Invention Instructions (65) 1 1 The concentration of inhibitors in the table is the value relative to the weight of zinc 0 white body The discharge rate is 1 1 maintained at 60 ° C for 2 days after measurement. It is said that it is equivalent to 1 year. The discharge rate of the white body after partial discharge is 50% deep discharge (partially please 1 I discharge) at 60 ° c Place 2 0 and measure it. Discharge-a- / · »first read 1 1 Measure the closed-circuit voltage 1 of 0 and do not add the inhibitor at _ 1 0 ° c after charging 1 (Example 1 5 4 6 9 and 8 4 in Table 1 5 Note 1 1 and Example 1 0 0 1 1 in Table 1 6 5 and 1 3 0) Compare the addition of inhibitors and then fill 1 The white body discharge rate of the preparation is small 0 As for partial discharge, if you add a coating to write this page | Cathode can (copper) such as indium sulfate and lead monoxide will improve White body put V_ 1 I electrical rate 〇 The closed circuit voltage of those who are known to add barium hydroxide becomes higher 0 Known from the attached table 1 1 | White body discharge before discharge when adding coated inhibitor and barium hydroxide 1 1 Order 1 The white body discharge rate and closed circuit voltage after partial discharge are improved. In this case, the reverse of the partial discharge occurs in the reverse of the case of using amalgam zinc. 1 1 The voltage is more than the discharge if-commercial phenomenon. The reason is huge. Still to be studied 〇1 I on the cathode The plating method is the same as that in Example 2 2. The results of β m on each film thickness 0 3 are shown. Even if the film thickness is 0 1 — 1 β m, the difference in results is still very small. In addition, K 0 Η type electrolyte and plating are used. The cathode can of indium is measured with respect to 1 1 1 inhibitor concentration. The white body discharge rate after 1 year and the partial discharge white 1 1 body discharge rate 〇1 | The results are shown in Figures 1 3 and 1 4 0 as long as the tributary range is not More than about 3% of the white body put 1 I electric power &gt; it is found that the effective range of indium sulfate is 5 0-5 0 0 0 1 1 1 PP M &gt; lead monoxide is 2 0-5 0 0 0 P Ρ m hydrogen Barium oxide is not less than 1 1 less than 5 0 PP m 9 and gas carbide-polyethylene oxide surfactant 1 1 This paper size is applicable to China National Standard (CNS) A4 specifications (2l〇X 297 mm) _ 68-A 7 B7 V. Description of the invention (66) No less than 100 p pm (relative to zinc concentration). As for the self-discharge rate after 50% deep discharge, the effective range is indium sulfate 50-5000ppm, and monoxide 20-5000ppm. After partial discharge, barium hydroxide and fluorocarbon-polyoxyethylene series surfactants are less effective. The results of indium sulfate in the indium compound are shown, but other compounds in the substantially same range are also effective. In addition, even if the electrolytic solution of the NaOH series and other cathode cans are used for plating, the effective concentration of the inhibitor is still substantially the same. Example 2 5-2 9 illustrates the effects of combining various technologies. In Examples 22-24, compositions using varying surfactants were evaluated. During the trial production of the battery, the type of zinc is also changed. "Before actually evaluating the characteristics of the battery, use a special test tube to evaluate the amount of hydrogen produced by each inhibitor and the electroplated copper plate." The method used is described below at a volume of 25mj? A special test tube of the amount of gas generated was pre-placed with 2 g of zinc powder containing bismuth, indium and lead made by a spray method of 500 p pm each, and a copper sheet with an area of 0.6 cm2 and a thickness of 0.1 mm ( The material is the same as the collector), add the electrolyte solution used for the test and heat to 60 ° C 'to measure the volume of hydrogen produced over 7 days. The test was repeated 10 times and the result was the average value. The preparation method of electrolyte solution is, if it is potassium hydroxide series, then add nearly saturated zinc oxide in 30% potassium hydroxide solution. If it is sodium hydroxide series, add it in 25% sodium hydroxide solution. Nearly saturated zinc oxide is used as a matrix and inhibitors are added at will. This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm) (please read the precautions on the back before filling in this page) -'β Printed by Beigong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs-69-Central Ministry of Economic Affairs Printed by the Bureau of Standards and Staff Consumer Cooperative A7 B7 V. Description of the invention (67) &lt; Example 2 5 &gt; At the same time, electroplated and substituted electroplated copper plates and inhibitors were used to measure the hydrogen produced by zinc. The plating process is as follows. * Indium (I η) electroplating method: electroplating ammonium bath:

: Indium sulfate 60g / Sense: Sodium sulfate 1 0 g / 2 5 ° C Coating thickness: 0 · 3 / zm * Tin (S η) Plating method: Electroplating bath:: Potassium stannate 100g / Another: Potassium hydroxide 15g / 5: Potassium acetate 5g / 70. . Coating thickness: 0.3 # m * Zinc indium (Zn_In) plating method: contact plating (copper plate and zinc are placed in a plating bath heated to below 60 ° C and placed for 1 hour) Plating bath: KOH 30%: Zn η 0 saturated : Indium sulfate 0.3% This paper scale is applicable to the Chinese National Standard (CNS) Α4 specification (210Χ297mm) A binding ί · ν &lt; (please read the precautions on the back before filling in this page) -70-A7 B7 V. Description of invention (68) Coating thickness: 0.3em The electroplated product on the copper plate and the hydrogen generation relative to the inhibitor are shown in Table 17 (using KOH series) and Table 18 (using NaOH series). The inhibitor concentration is expressed as a value relative to the electrolyte solution. (Please read the precautions on the back before filling out this page)

, 1T Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs

A

7 B V. Description of the invention (69) Table 1 7 · Hydrogen release rate of plated copper plate Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy Experiment number of plating type Electrolyte suppression rate (concentration: 100ppm) Hydrogen generation rate PL / g / Said 1 In KOH — 31.43 2 In KOH indium sulfate 14.28 3 In KOH gas-based indium acid expansion 12.41 4 In KOH indium hydroxide 16.73 5 In KOH lead oxide 17.85 6 In KOH barium hydroxide 8.57 7 In KOH P0ERA 8. 42 8 Sn KOH — 35.78 9 Sn KOH indium sulfate 16.11 10 Sn KOH indium sulfamate 17.72 11 Sn KOH indium hydroxide 16.53 12 Sn KOH lead oxide 17.91 13 Sn KOH barium hydroxide 10.89 14 Sn KOH P0ERA 10.02 15 Zn * In KOH — 32.34 16 Zn * In KOH indium sulfate 15.27 17 Zn · In KOH indium sulfamate 13.35 18 Zn * In KOH hydroxide 18.83 19 Zn * In KOH lead oxide 16.82 20 Zn · In KOH barium hydroxide 11.30 2 1 Zn * In KOH P0ERA 10.98 The size of this paper is in accordance with Chinese National Standard (CNS) A4 (210X297mm) (please read the precautions on the back before filling in this page), 一 = ° Γ 72-

A7 7 B V. Description of invention (7〇) Table 1 8 • Hydrogen release rate of electroplated copper plate Printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economy Experiment number Plating type Electrolyte inhibition rate (concentration: 100 ppm) Hydrogen generation rate ML / g / Yue 22 In NaOH — 29.41 23 In NaOH Indium sulfate 14.75 24 In NaOH Indium sulfamate 10.58 25 In NaOH Indium hydroxide 15.37 26 In NaOH Lead oxide 14.14 27 In NaOH Barium hydroxide 7.82 28 In NaOH P0ERA 8.13 29 Sn NaOH — 30.10 30 Sn NaOH indium sulfate 15.03 31 Sn NaOH indium sulfamate 15.28 32 Sn NaOH indium hydroxide 15.38 33 Sn NaOH lead oxide 14.53 34 Sn NaOH barium hydroxide 8.72 35 Sn NaOH P0ERA 9.52 36 Zn * In NaOH — 32.83 37 Zn * In NaOH indium sulfate 14.98 38 Zn * In NaOH indium sulfamate 13.19 39 Zn · In NaOH indium hydroxide 14.13 40 Zn · In NaOH lead oxide 14.27 41 Zn · In NaOH barium hydroxide 8.98 42 Zn · In NaOH P0ERA 8.95 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (21 OX 297 mm) (please read the precautions on the back before filling this page), τ Γ -73-A7 _B7 5. Description of the Invention (71) acyl polyoxyethylene alkyl amine (tables and figures to represent Ρ square E RA) by which two polyethylene oxide (POE) via Amides bonded to a nitrogen of the group. In this case, those having an alkyl carbon number of 11 and a POE polymerization degree of 15 are used. Generally, the same effect is obtained when the alkyl group has a carbon number of 3 to 30 and the POE polymerization degree is 2 to 50. Compared with those who do not add an inhibitor, the addition of the inhibitor of the present invention reduces the amount of hydrogen generated to about 1/3 to 1/2, so the effect of suppressing the generation of hydrogen is known. The difference due to plating or inhibitors is not significant. In addition, the amount of hydrogen generated relative to the test number is shown in Fig. 15 using the measurement results of indium-plated copper plates. Among indium compounds, only indium sulfate is shown in the figure. In this example, the results obtained using a plating thickness of 0.3 are shown. However, in practice, the difference between the results of the thickness of 0.1 mm and 1 mm is extremely small. &lt; Comparative Example 3 &gt; For comparison purposes, an electroless copper plate was used for the experiment according to the method of Example 25. The experimental results are shown in Table 19 and Figure 16. (Please read the precautions on the back and then fill out this page) Binding · Order The paper standard printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs applies the Chinese National Standard (CNS) A4 specification (210X 297 mm) -74-A7 B7 5. 2. Description of the invention (72) Table 1 9. Hydrogen release rate of unplated copper plate Electrolyte inhibitor printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (concentration: hydrogen generation rate 100 ppm) μ L / g / day 1 Κ0Η — 516.00 2 Κ0Η Indium sulfate 30.56 3 Κ0Η Indium sulfamate 28.73 4 Κ0Η Indium hydroxide 29.07 5 Κ0Η Lead oxide 24.15 6 Κ0Η Barium hydroxide 480.32 7 Κ0Η Carbon fluoride · P 0 E 432.19 Known not to add inhibitors When adding barium hydroxide or fluorocarbon-polyoxyethylene series surfactants, the amount of hydrogen generated increases exponentially with the number of test days. On the other hand, it is known that the addition of indium sulfate and lead oxide suppresses the generation of hydrogen gas. This is because the indium or lead compound has the function of coating the copper plate, but the paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) (please read the precautions on the back before filling in this page). 75-A7 B7 5. Description of the invention (73) Barium hydroxide and surfactant do not have this function. &lt; Example 2 6 &gt; A copper plate electroplated in the same manner as in Example 25 was used, and the amount of hydrogen gas generated by combining the inhibitors was measured using a K Ο Η series electrolyte solution. The results are shown in Table 20 (please read the precautions on the back before filling in this page). Binding and ordering The printed paper size of the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. The standard of the Chinese National Standard (CNS) Α4 specification (210 × 297 mm) 76 -8 ϋ 5 9 Qv οί B7 V. Description of the invention (74) Table 2 0 · Release rate of indium-plated copper plate and indium hydrogen The experimental inhibitor concentration PP m hydrogen production rate number is printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs Indium sulfate oxidation boat indium hydroxide P0ERA hL / g / day 43 100 100 0 0 15.82 44 100 0 100 0 10.10 45 100 0 0 100 12.28 46 0 100 100 0 14.64 47 0 100 0 100 15.40 48 0 0 100 100 9. 28 49 100 100 100 0 14.87 50 100 100 0 100 12.12 5 1 100 0 100 100 8.88 52 100 100 100 100 8.54 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297 mm) (please read the back (Notes and fill in this page again) 11.11 丨, τ Γ i -77-Printed by the Ministry of Economic Affairs, Central Bureau of Industry and Commerce Beigong Consumer Cooperative A7 B7 V. Description of the invention (75) The inhibitor column in the table shows the relative electrolyte solution Of inhibitors added concentration. It is known that the amount of generated hydrogen gas is extremely low as in the example, and even if various inhibitors are used, the effect is not too bad. In particular, the addition of barium hydroxide and poly (vinylalkylamide) simultaneously produces less hydrogen. Second, the battery was actually produced, and the plating effect and inhibitor effect on the collector were evaluated. "&Lt; Example 2 7 &gt; A part of the electrolyte solution and 116 mg were added to the anode can and the combination agent was added to the silver oxide and molded The particles (silver oxide content 98%), and placed polyethylene separator and cellophane separator. Next, push the nylon pad into the anode tank, add penetrant, gelling agent, 30mg zinc powder, inhibitor, etc., add the rest of the electrolyte solution with the inhibitor added drop by drop, and place the cathode seal to produce 10 0 various button-type silver oxide batteries. The zinc powder used is one containing 1300 p pm bismuth, 500 p pm indium and 30 ppm aluminum (made by spray method). The type and thickness of the plating on the cathode can, the type and concentration of the added inhibitor, the closed circuit voltage and the self-discharge rate are shown in Tables 21 and 22. The size of this paper is applicable to the Chinese National Standard (CNS) A4 (210X297mm) (please read the precautions on the back before filling in this page)

, 1T -78-A7

7 B V. Description of the invention (76) Printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs. 21 • Battery characteristics using K Ο Η electrolyte test number. Electrolyte type inhibitor concentration ppm Self-discharge rate% closed circuit voltage V indium sulfate hydrogen oxide Barium oxide POERA New battery partially discharged battery New battery partially discharged battery 53 — 0 0 0 0 0 5.8 9.9 1.158 1.179 54 In 0 0 0 0 4.3 5.9 1.165 1.192 55 In 1000 0 0 0 2.7 2.7 1.169 1.198 56 In 0 1000 0 0 2.7 2.8 1.168 1.197 57 In 0 0 1000 0 2.5 4.9 1.186 1.198 58 In 0 0 0 1000 2.6 5.0 1.165 1.185 59 In 1000 1000 0 0 2.5 2.6 1.168 1.197 60 In 1000 0 1000 0 2.4 2.6 1.186 1.239 61 In 1000 0 0 1000 2.4 2.5 1.168 1.199 62 In 0 1000 0 1000 2.4 2.6 1.168 1.197 63 In 0 1000 1000 0 2.6 2.7 1.167 1.238 64 In 0 1000 1000 1000 2.4 2.4 1.188 1.239 65 In 1000 1000 1000 0 2.6 2.6 1.186 1.240 66 In 1000 1000 0 1000 2.5 2.6 1.170 1.200 67 In 1000 0 1000 1000 2.3 2.3 1.185 1.240 68 In 1000 1000 1000 1000 2.4 2.4 1.186 1.238 69 Sn 0 0 0 0 4.7 6.8 1.167 1.193 70 Sn 1000 0 0 0 2.8 2.7 1.168 1.198 71 Sn 0 1000 0 0 2.7 2.8 1.170 1.199 72 Sn 0 0 1000 0 2.6 5.0 1.187 1.199 73 Sn 0 0 0 1000 2.6 5.1 1.165 1.185 74 Sn 1000 1000 0 0 2.6 2.7 1.168 1.197 75 Sn 1000 0 1000 0 2.4 2.5 1.187 1.240 (Please read the precautions on the back before filling in this page) r &gt; w, τ Γ i This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (2 丨 Ο X 297 Mm) -79-

AB Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (77) Table 2 1 (continued) Experiment number Electrolyte surface inhibitor concentration ppm White body discharge rate% Closed circuit voltage V Indium sulfate lead oxide barium hydroxide POERA New Battery Partially discharged battery New battery Partially discharged battery 76 Sn 1000 0 0 1000 2.4 2.4 1.168 1.201 77 Sn 0 1000 0 1000 2.4 2.6 1.169 1.196 78 Sn 0 1000 1000 0 2.7 2.8 1.167 1.240 79 Sn 0 1000 1000 1000 2.6 2.5 1.189 1.240 80 Sn 1000 1000 1000 0 2.7 2.6 1.185 1.240 81 Sn 1000 1000 0 1000 2.5 2.6 1.172 1.200 82 Sn 1000 0 1000 1000 2.3 2.6 1.186 1.241 83 Sn 1000 1000 1000 1000 2.4 2.5 1.188 1.241 84 Zn · In 0 0 0 0 4.9 7.1 1.171 1.199 85 Zn · In 1000 0 0 0 2.6 2.7 1.167 1.197 86 Zn. In 0 1000 0 0 2.9 3.0 1.188 1.200 87 Zn · In 0 0 1000 0 2.6 5.0 1.166 1.186 88 Zn · In 0 0 0 1000 2.6 5.0 1.168 1.197 89 Zn · In 1000 1000 0 0 2.5 2.6 1.186 1.239 90 Zn · In 1000 0 1000 0 2.5 2.7 1.169 1.200 91 Zn In 1000 0 0 1000 2.4 2.7 1.168 1.199 92 Zn · In 0 1000 0 1000 2.5 2.5 1.168 1.237 93 Zn In 0 1000 1000 0 2.6 2.9 1.188 1.241 94 ZnIn 0 1000 1000 1000 2.5 2.5 1.187 1.241 95 Zn In 1000 1000 1000 0 2.5 2.6 1.169 1.200 96 ZnIn 1000 1000 0 1000 2.7 2.6 1.187 1.240 97 Zn · In 1000 0 1000 1000 2.4 2.6 1.187 1.239 98 Zn · In 1000 1000 1000 1000 2.5 2.6 1.188 1.240 (please read the precautions on the back before filling in this page), τ This paper size applies to Chinese national standards (CNS) A4 specification (210X 297 mm) -80-A7 V. Description of invention (78) Printed form 2 of the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 2 2. Battery characteristics test number using N a ΟΗ electrolyte Concentration ppm Self-discharge rate% Closed circuit voltage V Indium sulfate lead oxide barium hydroxide POERA New battery partially discharged battery New battery partially discharged battery 99 — 0 0 0 0 5.5 9.6 1.157 1.181 100 In 0 0 0 0 4.0 5.5 1.167 1.194 101 In 1000 0 0 0 2.3 2.3 1.169 1.199 102 In 0 1000 0 0 2.2 2.5 1.169 1.198 103 In 0 0 1000 0 2.2 4.7 1.185 1.199 104 In 0 0 0 10 00 2.2 4.8 1.166 1.184 105 In 1000 1000 0 0 2.1 2.3 1.169 1.199 106 In 1000 0 1000 0 1.9 2.2 1.188 1.240 107 In 1000 0 0 1000 1.9 2.2 1.168 1.200 108 In 0 1000 0 1000 2.1 2.4 1.167 1.199 109 In 0 1000 1000 0 2.2 2.4 1.169 1.238 110 In 0 1000 1000 1000 1.8 1.9 1.189 1.240 111 In 1000 1000 1000 0 2.4 2.2 1.187 1.241 112 In 1000 1000 0 1000 2.2 2.1 1.171 1.202 113 In 1000 0 1000 1000 2.0 2.2 1.186 1.240 114 In 1000 1000 1000 1000 2.0 2.0 1.188 1.240 115 Sn 0 0 0 0 4.4 6.4 1.169 1.195 116 Sn 1000 0 0 0 2.5 2.2 1.169 1.200 117 Sn 0 1000 0 0 2.5 2.3 1.170 1.200 118 Sn 0 0 1000 0 2.4 4.7 1.189 1.200 119 Sn 0 0 0 1000 2.3 4.7 1.167 1.184 120 Sn 1000 1000 0 0 2.2 2.1 1.169 1.196 121 Sn 1000 0 1000 0 2.1 2.3 1.188 1.240 (Please read the precautions on the back before filling this page) r '', τ Γ 4- This paper size is applicable to China National Standard (CNS) A4 Specification (210X297mm) 81

7 7 AB Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of the invention (79) Table 22 (continued) Experiment number Type of electrolyte Inhibitor concentration ppm Self-discharge rate% Closed circuit voltage V Indium oxysulfate barium hydroxide P0ERA new battery Partially discharged battery New battery Partially discharged battery 122 Sn 1000 0 0 1000 1.9 2.1 1.169 1.200 123 Sn 0 1000 0 1000 2.2 2.3 1.168 1.198 124 Sn 0 1000 1000 0 2.5 2.4 1.169 1.240 125 Sn 0 1000 1000 1000 2.4 2.2 1.190 1.240 126 Sn 1000 1000 1000 0 2.4 2.3 1.186 1.241 127 Sn 1000 1000 0 1000 2.3 2.4 1.174 1.199 128 Sn 1000 0 1000 1000 2.0 2.4 1.186 1.241 129 Sn 1000 1000 1000 1000 2.1 2.2 1.89 1.241 130 ZnIn 0 0 0 0 4.6 6.7 1.172 1.201 131 Zn In 1000 0 0 0 2.3 2.3 1.169 1.198 132 Zn · In 0 1000 0 0 2.7 2.5 1.188 1.201 133 Zn · In 0 0 1000 0 2.4 4.8 1.168 1.187 134 Zn In 0 0 0 1000 2.3 4.8 1.170 1.197 135 Zn · In 1000 1000 0 0 2.1 2.4 1.188 1.240 136 Zn · In 1000 0 1000 0 2.2 2.4 1.170 1.199 137 Zn · In 1000 0 0 1000 2.2 2.5 1.169 1.1 99 138 Zn In 0 1000 0 1000 2.2 2.2 1.167 1.236 139 ZnIn 0 1000 1000 0 2.1 2.6 1.187 1.243 140 Zn In 0 1000 1000 1000 2.3 2.0 1.187 1.242 141 ZnIn 1000 1000 1000 0 2.3 2.4 1.168 1.201 142 Zn In 1000 1000 0 1000 2.2 2.4 1.189 1.241 143 ZnIn 1000 0 1000 1000 2.2 2.4 1.187 1.240 144 ZnIn 1000 1000 1000 1000 2.3 2.3 1.187 1.241 This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) -82-Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A 7 B7 V. Description of invention (80) The inhibitor concentration in the table is relative to zinc The value of weight. The self-discharge rate is measured at 60 ° C for 20 days. It is said to be equivalent to 1 year. The self-discharge rate after partial discharge was measured after 50% deep discharge (partial discharge) at 60 ° C for 20 days. Before and after partial discharge, measure the closed circuit voltage at –10 ° C. Compared with those who did not add inhibitors (Examples 5, 4, 9 and 8 4 in Table 15 and Examples 100 in Table 22, '115 and 130), the self-discharge rate of the inhibitors was small. As for partial discharge, if a cathode can (copper) coating such as indium sulfate and lead monoxide is added, the self-discharge rate is improved. It is known that the closed circuit voltage of those who add barium hydroxide becomes high. According to the attached table, the self-discharge rate before discharge, the self-discharge rate after partial discharge, and the closed circuit voltage are improved when the coating type inhibitor and barium hydroxide are added. In this example, contrary to the case of using amalgam zinc, the closed circuit voltage after partial discharge is higher than before discharge. The reason is still to be studied. The electroplating method on the cathode is the same as in Example 25, showing the results of each film thickness 0.3. Even if the film thickness is 〇.1-l # m, the difference in results is still very small. <Example 28> In addition, batteries were produced using KO H-type electrolytes and indium-plated cathode cans, and the concentration of the inhibitor was measured over 1 year The self-discharge rate after the partial discharge and the self-discharge rate after the partial discharge. The results are shown in Figures 17 and 18. According to Figure 17, as long as the actual range is not greater than about 3% of the self-discharge rate, the effective range of indium sulfate is found to be the paper standard applicable to the Chinese National Standard (CNS) Α4 specification (210Χ 297 mm) (please read the notes on the back first Please fill in this page again) -'9 -83-Ο 508 A7 B7 V. Description of the invention (81 5 0- Ρ Ρ m is not less than the effective range 20-Ethylene electrical conductivity, barium-polyenamine demand compound In addition, in addition to plating, but 5 0 0 0 0, 5 ρ ρ OH in 5 0 surrounding sulfuric acid 5 0 0 0 Alkylamide has been found that the oxidizable ethylene does not exceed 1, but, even if the inhibitor ppm A lot of barium m (phase% depth indium 50 ppm is more effective than the effective group alkylamide 0 0 0 Yes, it is effective with Na a concentrated lead monoxide is 20-5000 ethylene oxide alkylamide is less than 50 for zinc P P m , The concentration of poly). The self-discharge rate after discharge, root 0 0 ρ pm, and -50 after one minute discharge. Not large in part. Combined use. But ppm other compounds Ο Η type degree range is to reduce part of indium sulfate or One, use in combination. The result is that the effective concentrated electrolyte solution of the substance is substantially the same. After discharge, the sulfuric acid range of lead oxide polyoxygen or other according to Figure 18. The self-discharge of lead barium oxide and polyoxygen and the oxidation of ethylene alkane are the same as the cathode can. (Please read the precautions on the back first (Fill in this page) Ordered by the Ministry of Economic Affairs, Central Bureau of Standards, Consumer Cooperative Printing &lt; Example 2 9 &gt; The zinc composition was changed as in Example 2 7 to trial-produce the battery. Use ΚΟΗ type electrolyte solution and indium plating on the cathode can The agent is indium sulfate, lead monoxide, barium hydroxide, and polyoxyethylene acetylamine relative to zinc at 1000 p pm each. The results are shown in Table 2. 3. The paper scale is applicable to the Chinese National Standard (CNS) ) A4 specification (210X297 company director) -84-

A

7 B V. Description of the invention (82) Table 2 3. Battery characteristics with KOΗ electrolyte Printed by the Ministry of Economic Affairs Central Standards Bureau Employee Consumer Cooperative Printed experiment Metal concentration added to zinc PP m Self-discharge rate% Closed circuit voltage V number P b B i In A 1 C a New battery partially discharged battery New battery partially discharged battery 145 500----2.9 2.8 1.186 1.200 146 500 50---2.8 2.8 1.187 1.235 147 500-— 250-2.8 2.7 1.186 1.235 148 500 500 500--2.3 2.5 1.186 1.234 149 10 100 515 30-2.7 2.7 1.188 1.222 150 23 240---2.9 2.9 1.189 1.200 151 28 240 1780--2.5 2.6 1.189 1.240 152-140 480--2.4 2.6 1.185 1.239 153-130 500 30 ~ 2.4 2.4 1.186 1.238 154-130 500-50 2.3 2.4 1.188 1.236 The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X 297mm) (Please read the notes on the back before filling this page ),-° Γ j -85-Printed by the Employee Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economy V. Description of Invention (83) Obviously included in the composition of additives defined in the scope of patent application, included in Self discharge rate within the range of not more than 3 occasion%. In order to reduce the self-discharge rate, various alloys need to be formed. Examples 3 0-3 1 are the main evaluation results of the combined gelling agent. &lt; Example 3 0 &gt; The hydrogen production test was used to determine the effect of the present invention before the actual production of the battery. A composition of zinc powder, the gelling agent of the present invention, barium hydroxide and a copper plate which is the same as the collector material is used. Pre-add 2 g of zinc powder (containing bismuth, indium and lead prepared by spray method at 500 p pm each) in a special test tube with a volume of 25 mj? Heat to 60 ° C and measure the volume of hydrogen produced for 7 days. Use 2 g of zinc powder and five copper sheets with the same material as the collector and an area of 0.6 cma and a thickness of 0.1 mm to make the ratio of cathode zinc weight to the surface area of the cathode collector of the battery the same. Repeat the test 6 times and take the average value as the result. The preparation method of the electrolyte solution is that if it is a potassium hydroxide system, add near-saturated zinc oxide to the 30% potassium hydroxide solution, if it is a sodium hydroxide series, add it to the 25% sodium hydroxide solution Nearly saturated zinc oxide is used as a matrix and barium hydroxide is added. Barium hydroxide made by Wako Pure Chemical Industries., Ltd. was used, CMC was N. 1 2 6 0 and No. 1380 made by icel Chemical Industries, Ltd., and PAS was Wako Pure Chemical In- The reagents made by dustries., Ltd., and Rheogic 2 50 H are made by Nihon Pure Chemicals Co., Ltd. Addition of barium hydroxide The standard of this paper is the Chinese National Standard (CNS) Α4 specification (210X297mm) (please read the precautions on the back before filling this page), -β

T -86-Printed by the Staff Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 V. Description of invention (84) The amount added is 9 to 5 0 0 0 p pm relative to the electrolyte solution. The results of hydrogen production are shown in Table 24. The size of this paper is applicable to China National Standard (CNS) A4 specification (210X 297mm) -------- "installed ------ ordered ------ {k (please read the note on the back first Please fill in this page again) -87-

Claims (1)

209508 A8 B8 C8 D8 VI. Scope of patent application 1. One, including: powder, which is a cathode active material-material; and (please read the precautions on the back before filling this page) Electro-hydraulic 'The electro-hydraulic solution Following ϋ or Dad is very much selected from New Food Group's compound containing Xibei-E3 valence, and Oxygen | compounds. 2 · As for the alkaline battery in the first item of the patent application scope, in which the indium compound is sulfuric acid J0, amine group and _acid shoulder, chlorobutanol and Xifubei marriage 3. As in the patent application of the first item鹸 性 電 性 電, of which the tetravalent sugar compound is based on argon gas such as: potassium stannate., House _ acid. Plate, etc. and tin oxide "4. One, including: v no-Li H" This is Yong Extremely. Inclusive material, cathode jg. In this material-Li Ji Di _ ^ _ multi-,. MJ1 self-propelled material, contains a superior price of .. tin | compounds, and lead oxide compounds. 5. A ponari battery as claimed in item 4 of the patent application, wherein the indium compound ill is indium sulfate, indium sulfamate, indium chloride and indium hydroxide. 6. An alkaline battery as claimed in item 4 of the patent application, wherein the battery belongs to the explosive type stannate such as potassium stannate, sodium stannate, etc. and tin oxide. _ 一 ~ ^ 7. —A variety of application products that use test batteries, including: ψ- Printed by the Employee Consumer Cooperative of the Central Standard Falcon Bureau of the Ministry of Economic Affairs, which is a cathode active material; and wing liquid, which is good and good Add _ or _ support species to the turbidity. Choose _ from the indium-containing food ~ .._, ..._ ^ _ 1 valence .. argon-. Tin "dagger compound ..._, and lead oxide ϋ Thing. -Guangzhou 8.-A variety of application products that use chrysanthemum batteries, including: Lost I powder, which is a cathode active material, article two. Add two to the tile material, or. Chawu is selected from the North, containing. .Price. Xi Li Ao Bei "^ Things, and Compounds" This paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297mm_) _ 88 ~