CN1348224A - Indium plating method for copper nail of negative current collector of mercury-free alkaline zinc-manganese dioxide battery - Google Patents
Indium plating method for copper nail of negative current collector of mercury-free alkaline zinc-manganese dioxide battery Download PDFInfo
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- CN1348224A CN1348224A CN01129898A CN01129898A CN1348224A CN 1348224 A CN1348224 A CN 1348224A CN 01129898 A CN01129898 A CN 01129898A CN 01129898 A CN01129898 A CN 01129898A CN 1348224 A CN1348224 A CN 1348224A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to an indium plating method for a copper nail of a cathode current collector of a mercury-free alkaline manganese battery, belonging to the battery preparation technology. The method comprises the following steps of (1) chemical degreasing, namely preparing a chemical degreasing agent, putting a copper nail substrate into the degreasing agent for degreasing, and cleaning the copper nail substrate with deionized water after degreasing, (2) chemical polishing, namely preparing polishing solution, putting the copper nail cleaned after chemical degreasing into the polishing solution, cleaning with clear water after polishing, and immediately electroplating, (3) vibration indium plating, namely preparing electroplating solution according to a certain formula ratio, putting the polished copper nail into a vibration plating machine for electroplating under certain process conditions, wherein the anode uses metal indium or graphite, and (4) vibration polishing, namely washing the electroplated copper nail, putting the polished copper nail into a vibration polishing machine for polishing, cleaning with deionized water after polishing, and drying with a centrifugal dryer, so as to obtain the negative current collector indium plated copper nail for the alkaline zinc-manganese battery. The invention has simple process and easy realization, the prepared product has bright and smooth coating, and is easy to be transported on a battery production line, and all indexes of the produced battery are superior to the level of the existing battery.
Description
The technical field is as follows:
the invention relates to a method for plating indium on a copper nail of a cathode current collector of a mercury-free alkaline zinc-manganese dioxide battery, belonging to the battery preparation technology.
(II) background technology:
the zinc-manganese cell is the least expensive of all the cells, so it is the most widely used cell. In zinc-manganese batteries, alkaliAlthough the production cost of the zinc-manganese battery is higher than that of the common carbon-zinc battery, the alkaline zinc-manganese battery can particularly meet the requirements of consumers in modern society due to the large output power and high discharge capacity characteristic, and the alkaline zinc-manganese battery becomes a mainstream product of a small battery along with the successful development of the rechargeable alkaline zinc-manganese battery. One of the major problems with conventional alkaline zinc-manganese batteries is the use of mercury. Today, people have higher and higher requirements on the quality of living environment and stronger requirements on reducing environmental pollution. Mercury and compounds thereof serving as efficient battery zinc cathode corrosion inhibitors are used in alkaline zinc-manganese batteries all the time, but mercury causes serious environmental pollution, and the mercury-free alkaline zinc-manganese batteries are necessary requirements for social development. Mercury plays an important role in improving the performance of alkaline zinc manganese batteries. Mercury has a high hydrogen evolution overpotential and at the same time it is prone to amalgam with other metals. In the alkaline zinc-manganese battery, mercury, negative zinc powder and a current collector copper nail form amalgam to inhibit hydrogen separation and zinc corrosion; mercury is the only liquid metal, and can improve the dissolution activity of zinc during battery discharge, reduce the contact resistance between negative zinc powder and between the zinc powder and a current collector, and improve the anti-seismic performance of the battery. Therefore, the technical difficulty is great for leading the battery to be mercury-free and keeping the good performance of the battery; the main measure for the mercury-free alkaline zinc-manganese battery is to find a suitable corrosion inhibitor. However, regardless of the combination, indium is an essential component; the mercury-substituting function of indium in the alkaline zinc-manganese dioxide battery is mainly as follows: (1) increasing hydrogen discharge overpotential. Indium belongs to metal with higher hydrogen discharge overpotential, only lead, cadmium, mercury, thallium and indium with higher hydrogen discharge overpotential than zinc belong to metal harmful to the environment like mercury, so indium is the only practical element with higher hydrogen discharge overpotential than zinc; and (2) improving the activity of zinc. Indium readily alloys with zinc and, like mercury, increases the zinc stability by increasing its equilibrium potential. More importantly, however, after the surface of the zinc powder is indium, zinc is eluted from the indium layer,therefore, the indium plays a role of mercury, thereby preventing the passivation of zinc and improving the active dissolution of the zinc; and (3) reducing the contact resistance of the negative electrode and improving the shock resistance of the battery. The most remarkable characteristic of indium is high plasticity, which enables good electrical contact between zinc powder with indium on the surface and between zinc powder and indium-plated current collector, especially when the battery is impacted due to indium changeThe shape of the cathode can ensure that the battery cathode has good electric contact, and the cathode has the similar effect of reducing the contact resistance with mercury and improving the shock resistance of the battery. Therefore, indium is an indispensable component for mercury-free alkaline zinc-manganese batteries; the usage of indium in alkaline zinc-manganese batteries is mainly in three forms: one is adding indium to prepare zinc-indium alloy when preparing zinc powder; secondly, indium trioxide or indium hydroxide is added into the alkali liquor, and the two use forms are successful in production practice; and the third is indium plating on the current collector. Indium plating has many advantages over tin plating on conventional copper nails. First, tin is easily oxidized in air, while indium is very stable in air. Indium is plated on metals such as tin, lead, cadmium and the like or alloys, so that the welding performance of the metals or the alloys is improved, and the oxidation resistance of the metals or the alloys is mainly improved, so that the battery produced by using indium-plated copper nails is less influenced by the environment and the operating conditions than tin-plated copper nails; secondly, the overpotential of hydrogen discharge on the indium is higher than that of zinc, while the overpotential of hydrogen discharge of the tin is lower than that of the zinc, so that the indium-plated copper nail can inhibit hydrogen discharge and reduce the self-discharge loss of a negative electrode, and the tin-plated copper nail can promote the corrosion of zinc powder to cause the self-discharge of a battery; again, the difference in conductivity between indium and tin, with the conductivity of tin being 11.3. Mu. Omega. Cm -1 Indium (8.5. Mu. Omega. Cm) -1 ) Because of high, the contact resistance between the indium-plated copper nail and the zinc powder is smaller than that between the tin-plated copper nail and the zinc powder; and indium is much softer than tin, and is easy to deform, so that the shock resistance of the battery can be improved, and the like. Unfortunately, current indium plating methods do not meet the requirements for battery use. The main problems are as follows: (1) Coating glossThe cleanliness is not high, and in battery production, the indium-plated copper nails are conveyed by a guide rail with high precision, and the plating layer is required to have high smoothness; (2) the plating layer is uneven, so that local matrix copper is easily exposed; and (3) the plating layer is not dense and does not play a role of covering copper.
(III) the invention content:
the invention aims to realize the mercury-free performance of the alkaline zinc-manganese battery, and researches and invents a mercury-free alkaline zinc-manganese battery cathode current collector copper nail indium plating method with no pollution and low cost by overcoming and solving the defects and problems of insufficient coating smoothness, uneven coating, non-compact coating and the like of the existing indium plating method.
The invention is realized by the following technical scheme: chemical degreasing: the copper nail matrix is placed in an oil removing agent at the temperature of 20-40 ℃ for 10-20 minutes to remove oil, and the oil removing agent is prepared by mixing the following components in percentage by weight: sodium carbonate Na 2 CO 3 2 to 4 percent of sodium phosphate Na 3 PO 4 ·12H 2 1 to 3 percent of O and Na sodium silicate 2 SiO 3 0.5 to 1 percent of emulsifier OP, 0.2 to 0.3 percent of emulsifier OP, 0.005 to 0.015 percent of sodium dodecyl sulfate, 91.685 to 96.295 percent of water, and is cleaned by deionized water after oil removal; (2) chemical polishing: the copper nail cleaned after chemical degreasing is put into polishing solution with the temperature of 10-40 ℃ for 30-60 seconds, and the polishing solution is prepared by mixing the following components in percentage by weight: sulfuric acid H 2 SO 4 30 to 60 percent of sodium nitrate NaNO 3 5 to 10 percent of sodium chloride NaCl0.2 to 1 percent of urea 4 to 6 percent of sodium chloride,0.1 to 0.2 percent of polyethylene glycol and 22.8 to 60.7 percent of water, and the mixture is washed by clean water after polishing and immediately plated; (3) vibrating indium plating: placing the polished copper nail into a vibration plating machine for electroplating, wherein the weight percentage formula and the process conditions of the electroplating solution are as follows: indium chloride InCl 3 2 to 5 percent of sodium chloride and 2 to 8 percent of NaClPercent, additive A0.1-0.5 percent, additive B0.001-0.01 percent, water 86.49-95.899 percent, temperature: 10-40 ℃, pH value of 2-4, cathode current density: 1 to 10A/cm 2 The voltage is 2-5V, the time is 5-20 minutes, and the anode uses metal indium or graphite; the additive A can be selected from the following phenols: p-benzenediol, resorcinol, naphthol; the additive B can be selected from ox gum, gelatin, and gum arabic; (4) vibration polishing: the copper nail after will electroplating washes cleanly, arranges the polishing in the vibrations burnishing machine, and the time: 5-30 minutes; and taking out the copper nail after polishing, cleaning the copper nail by using deionized water, and centrifugally drying the copper nail to obtain a negative current collector indium-plated copper nail product for the mercury-free alkaline zinc-manganese battery.
The method has simple process and easy realization, the coating of the product is bright and smooth, the product can be smoothly conveyed on a zinc-manganese battery production line, and the main performance indexes of the produced battery, such as short-circuit current, internal resistance, hydrogen evolution quantity and the like, are better than the level of the battery made of the tinned copper nail.
(IV) specific embodiments:
the inventors consider that it is simple and easy to implement the present invention, and the present invention can be preferably carried out by performing the stepwise operations according to the method, the steps, the formulation ratio and the process conditions described in the above description. The inventors have had many successful examples over the course of long-term research and experimentation, and the following list of only three examples is shown in Table 1 below. ZD-I type can be selected for the vibration plating machine in the implementation process; PG-T type can be selected as the vibration polishing machine; centrifugal drier LX-J type.Table 1:
Claims (1)
1. a method for plating indium on a copper nail of a cathode current collector of a mercury-free alkaline zinc-manganese dioxide battery is characterized by comprising the following steps: (1) Chemical degreasing: the copper nail matrix is placed in an oil removing agent at the temperature of 20-40 ℃ for 10-20 minutes to remove oil, and the oil removing agent is prepared by mixing the following components in percentage by weight: sodium carbonate Na 2 CO 3 2 to 4 percent of sodium phosphate Na 3 PO 4 ·12H 2 1 to 3 percent of O and Na sodium silicate 2 SiO 3 0.5 to 1 percent of emulsifier OP, 0.2 to 0.3 percent of emulsifier OP, 0.005 to 0.015 percent of sodium dodecyl sulfate, 91.685 to 96.295 percent of water, and is cleaned by deionized water after oil removal; (2) chemical polishing: the copper nail cleaned after chemical degreasing is put into polishing solution with the temperature of 10-40 ℃ for 30-60 seconds, and the polishing solution is prepared by mixing the following components in percentage by weight: sulfuric acid H 2 SO 4 30 to 60 percent of sodium nitrate NaNO 3 5 to 10 percent of sodium chloride NaCl0.2 to 1 percent of urea, 4 to 6 percent of urea, 0.1 to 0.2 percent of polyethylene glycol and 22.8 to 60.7 percent of water, and the mixture is washed by clean water after polishing and is immediately electroplated; (3) vibrating indium plating: placing the polished copper nail in a vibration plating machine for electroplating, wherein the weight ratio of the electroplating solution is as follows: indium chloride InCl 3 2 to 5 percent of sodium chloride, 2 to 8 percent of NaCl, 0.1 to 0.5 percent of additive A, 0.001 to 0.01 percent of additive B, 86.49 to 95.899 percent of water, and the temperature is as follows: 10-40 ℃, pH value of 2-4, cathode current density: 1 to 10A/cm 2 The voltage is 2-5V, the time is 5-20 minutes, and the anode uses metal indium or graphite; the additive A is selected from the following phenols: hydroquinone, resorcinol, naphthol; the additive B is selected from bovine gum, gelatin and Arabic gum; (4) vibration polishing: the copper nail after electroplating is washed clean, and is placed in a vibration polishing machine for polishing, and the polishing time is as follows: 5-30 minutes; and after polishing, taking out the copper nail, washing with deionized water, centrifuging and drying to obtain the negative electrode current collector indium-plated copper nail product for the mercury-free alkaline zinc-manganese dioxide battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011298987A CN1152444C (en) | 2001-11-09 | 2001-11-09 | Indium plating method for copper nail of negative current collector of mercury-free alkaline zinc-manganese dioxide battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011298987A CN1152444C (en) | 2001-11-09 | 2001-11-09 | Indium plating method for copper nail of negative current collector of mercury-free alkaline zinc-manganese dioxide battery |
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| CN1348224A true CN1348224A (en) | 2002-05-08 |
| CN1152444C CN1152444C (en) | 2004-06-02 |
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| CNB011298987A Expired - Fee Related CN1152444C (en) | 2001-11-09 | 2001-11-09 | Indium plating method for copper nail of negative current collector of mercury-free alkaline zinc-manganese dioxide battery |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427647C (en) * | 2005-10-14 | 2008-10-22 | 田鹏 | Thin electroplating solution of metal indium chloride/1-methyl-3-ethyl imidazole chloride |
| CN101956220A (en) * | 2010-11-02 | 2011-01-26 | 济南德锡科技有限公司 | Plating pretreatment oil remover composite and preparation and use methods thereof |
| CN102500581A (en) * | 2011-09-27 | 2012-06-20 | 余姚市中盛电子科技有限公司 | Cleaning process of copper needle of alkaline Zn/MnO2 battery |
| CN104087975A (en) * | 2013-12-19 | 2014-10-08 | 浙江工商大学 | Preparation method of foamed copper |
| CN105200434A (en) * | 2015-11-03 | 2015-12-30 | 江苏梦得电镀化学品有限公司 | High-brightness chemical polishing solution for copper and copper alloy |
| CN106876717A (en) * | 2017-04-17 | 2017-06-20 | 中银（宁波）电池有限公司 | Alkaline zinc-manganese battery current collector, manufacturing method thereof and leakage-proof alkaline zinc-manganese battery |
| CN110004470A (en) * | 2019-05-27 | 2019-07-12 | 南平华孚电器有限公司 | Roll plating indium production process of current collector copper needle |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270490B (en) * | 2008-04-11 | 2010-04-14 | 沈阳师范大学 | Dissipated metal indium chloride/chloridization 1-methyl-3-butyl imidazole system plating solution |
| EP2848714B1 (en) * | 2008-04-22 | 2016-11-23 | Rohm and Haas Electronic Materials LLC | Method of replenishing indium ions in indium electroplating compositions |
| CN102210736B (en) * | 2011-05-31 | 2013-02-20 | 安徽丰原淮海制药有限公司 | Medicine composition for treating tenosynovitis and preparation method thereof |
-
2001
- 2001-11-09 CN CNB011298987A patent/CN1152444C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427647C (en) * | 2005-10-14 | 2008-10-22 | 田鹏 | Thin electroplating solution of metal indium chloride/1-methyl-3-ethyl imidazole chloride |
| CN101956220A (en) * | 2010-11-02 | 2011-01-26 | 济南德锡科技有限公司 | Plating pretreatment oil remover composite and preparation and use methods thereof |
| CN102500581A (en) * | 2011-09-27 | 2012-06-20 | 余姚市中盛电子科技有限公司 | Cleaning process of copper needle of alkaline Zn/MnO2 battery |
| CN104087975A (en) * | 2013-12-19 | 2014-10-08 | 浙江工商大学 | Preparation method of foamed copper |
| CN105200434A (en) * | 2015-11-03 | 2015-12-30 | 江苏梦得电镀化学品有限公司 | High-brightness chemical polishing solution for copper and copper alloy |
| CN106876717A (en) * | 2017-04-17 | 2017-06-20 | 中银（宁波）电池有限公司 | Alkaline zinc-manganese battery current collector, manufacturing method thereof and leakage-proof alkaline zinc-manganese battery |
| CN110004470A (en) * | 2019-05-27 | 2019-07-12 | 南平华孚电器有限公司 | Roll plating indium production process of current collector copper needle |
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| CN1152444C (en) | 2004-06-02 |
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