CN1152444C - 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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- CN1152444C CN1152444C CNB011298987A CN01129898A CN1152444C CN 1152444 C CN1152444 C CN 1152444C CN B011298987 A CNB011298987 A CN B011298987A CN 01129898 A CN01129898 A CN 01129898A CN 1152444 C CN1152444 C CN 1152444C
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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 specific method comprises the following steps: chemical degreasing: preparing a chemical degreasing agent, namely putting the copper nail matrix into the degreasing agent for degreasing, and cleaning the copper nail matrix with deionized water after degreasing; (2) chemical polishing: preparing polishing solution, putting the copper nail which is cleaned after chemical degreasing into the polishing solution, cleaning the copper nail with clean water after polishing, and immediately electroplating; (3) vibrating indium plating: preparing electroplating solution according to a certain formula ratio, placing the polished copper nail in a vibration plating machine for electroplating under a certain process condition, and using metal indium or graphite as an anode; (4) vibration polishing: and (3) washing the electroplated copper nail, polishing in a vibration polishing machine, cleaning with deionized water after polishing, and drying by using a centrifugal dryer to obtain the indium-plated copper nail of the negative current collector 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 convey 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 an indium plating method for 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. Among zinc-manganese batteries, alkaline zinc-manganese batteries have higher production cost than ordinary carbon-zinc batteries, but can particularly meet the requirements of consumers in modern society due to the characteristics of high output power and high discharge capacity, and become the mainstream products of small batteries with the successful development of rechargeable alkaline zinc-manganese batteries. 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 corrosion inhibitors for zinc cathodes of batteries are used in alkaline zinc-manganese batteries all the time, but mercury can cause serious environmental pollution, and 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, it is required toThe battery is free of mercury and keeps good performance of the battery, and the technical difficulty is high; 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, can improve the stability of zinc by increasing its equilibrium potential. More importantly, after the surface of the zinc powder is indium, zinc is dissolved out from the indium layer, so that the indium plays a role of mercury, the passivation of the zinc is prevented, and the active dissolution of the zinc is improved; 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 cathode contact resistance and improving the battery shock resistance with mercury. Therefore, indium is an indispensable component for the mercury-free alkaline zinc-manganese battery: 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 plating on metals or alloys of tin, lead, cadmium, etc. in addition to improving the solderability of the metal or alloy, the main objective is to improve the oxidation resistance of the metal or alloy, and thus, to make the alloy more resistant to oxidationThe indium-plated copper nails are less affected by the environment and the operating conditions than the tin-plated copper nails are used for producing the battery; 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 conductivity difference between indium and tin, with the conductivity of tin being 11.3 μ Ω. Cm -1 Specific 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) The coating has low degree of finish, and in battery production, the indium-plated copper nails are conveyed by a guide rail with high precision, so that the coating is required to have high degree of finish; (2) the plating layer is uneven, so that local matrix copper is easily exposed; and (3) the plating layer is not dense and cannot cover copper.
(III) the invention content:
the invention aims to realize the mercury-free alkaline zinc-manganese battery, and researches and invents a mercury-free alkaline zinc-manganese battery cathode current collector copper nail indium plating method which is free of pollution and low in 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 OP0.2 to 0.3 percent of sodium dodecyl sulfate 0.0 percent05 to 0.015 percent of oil and 91.685 to 96.295 percent of water, and the oil is cleaned by deionized water after being degreased; (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 cleaned by clear water after being polished and is immediately electroplated; (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, 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: 1-10A/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 or naphthol; additive B can be selected from ox gum, gelatin or acacia; (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 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 believe that it is relatively simple and easy to implement the present invention, and that it can be better practiced by performing the steps and by using the methods, steps, formulation ratios and process conditions described in the above specification. 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 for the vibration polishing machine; centrifugal drier LX-J.
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: 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 OP0.2 to 0.3 percent, 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 cleaned by clear water after being polished and is immediately electroplated; (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 NaCl0.1-0.5% of additive A, 0.001-0.01% of additive B, 86.49-95.899% of water, and the temperature: 10-40 ℃, pH value of 2-4, cathode current density: 1-10A/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 or naphthol; the additive B is selected from bovine gum, gelatin or gum arabic; (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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| Publication Number | Publication Date |
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| CN1348224A CN1348224A (en) | 2002-05-08 |
| CN1152444C true CN1152444C (en) | 2004-06-02 |
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| Application Number | Title | Priority Date | Filing Date |
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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 (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 |
| CN101613865B (en) * | 2008-04-22 | 2011-06-08 | 罗门哈斯电子材料有限公司 | 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100427647C (en) * | 2005-10-14 | 2008-10-22 | 田鹏 | Thin electroplating solution of metal indium chloride/1-methyl-3-ethyl imidazole chloride |
| CN101956220B (en) * | 2010-11-02 | 2011-12-21 | 济南德锡科技有限公司 | Plating pretreatment oil remover composition 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 |
-
2001
- 2001-11-09 CN CNB011298987A patent/CN1152444C/en not_active Expired - Fee Related
Cited By (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 |
| CN101613865B (en) * | 2008-04-22 | 2011-06-08 | 罗门哈斯电子材料有限公司 | 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 |
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| CN1348224A (en) | 2002-05-08 |
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