CN1404175A - Surface treatment method for positive current collector of alkaline zinc-manganese battery with inner surface of cog structure - Google Patents
Surface treatment method for positive current collector of alkaline zinc-manganese battery with inner surface of cog structure Download PDFInfo
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- CN1404175A CN1404175A CN 02134740 CN02134740A CN1404175A CN 1404175 A CN1404175 A CN 1404175A CN 02134740 CN02134740 CN 02134740 CN 02134740 A CN02134740 A CN 02134740A CN 1404175 A CN1404175 A CN 1404175A
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- current collector
- alkaline zinc
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- steel cylinder
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Abstract
The invention provides a surface treatment method for an alkaline zinc-manganese battery anode current collector with a cog structure on the inner surface, which is characterized by comprising the following steps: chemical degreasing; (2) micro-etching and polishing; (3) Chemical nickel plating, wherein the microetching polishing is to place the steel cylinder which is cleaned after oil removal in a vibration polishing machine at room temperature, add microetching liquid and acid-resistant abrasive, and polish for 1-3 hours, and clean the steel cylinder with water after the microetching polishing; the invention has simple process and easy operation, the manufactured positive current collector with cog structure has bright and smooth outer surface, rough inner surface micropores and uniform coating thickness of the inner surface and the outer surface, and the alkaline zinc-manganese battery produced by the positive current collector increases the contact area of the manganese ring and the steel cylinder, so that the combination of the manganese ring and the steel cylinder is firmer, the contact resistance is smaller, and the capacity, the anti-seismic performance and the storage performance of the alkaline zinc-manganese battery can be obviously improved.
Description
Technical Field
The invention relates to a preparation technology of battery accessories, in particular to a surface treatment method for an alkaline zinc-manganese battery anode current collector with a cog structure on the inner surface.
Background
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 are now the mainstream products of small batteries. At present, the production methods of the positive current collector steel cylinder of the alkaline zinc-manganese battery mainly comprise two methods: (1) a drawing forming method of an electroplated nickel steel plate; and (2) electroplating nickel after the steel plate is stretched and formed. No matter which method is adopted, the inner surface of the positive current collector is smooth, so that the bonding force between the positive active material manganese ring and the steel cylinder is weak, the contact resistance is large, the anti-seismic performance of the battery is poor, and the current fluctuation or power failure is caused. In addition, since the first method has problems that a notch is easily rusted and a plating layer is torn at the time of stretch forming, most manufacturers adopt the second method. However, the difference between the current densities of the inner surface and the outer surface of the steel cylinder for nickel electroplating is too large, and the thicknesses of the inner surface and the outer surface of the steel cylinder for nickel electroplating often differ by several times or even dozens of times. Therefore, it is not feasible to increase the thickness of the plating film by simply extending the plating time so as to prevent the inner surface from rusting, because: (1) The internal diameter of the steel cylinder is reduced after the thickness is increased, a manganese ring cannot be arranged in the steel cylinder or is easy to break, and (2) the outer surface coating is too thick, so that brittleness is easy to cause, and the battery is easy to burst when finally sealed. Therefore, the currently adopted method is passivation and rust prevention treatment after plating, which inevitably causes the passivation film on the inner surface of the steel cylinder, thereby increasing the contact resistance of the battery, reducing the voltage of the battery, reducing the capacity and influencing the discharge performance; in addition, most of passive films can be dissolved in concentrated alkali, and the dissolution of the passive films can generate impurities to increase the self-discharge of the battery on one hand, and can reduce the binding force between a manganese ring and the inner surface, increase the resistance, reduce the anti-seismic performance and easily cause power failure on the other hand; moreover, after the passive film is dissolved, the positive active material can oxidize the inner surface of the steel cylinder, and if the internal surface of the steel cylinder is severe, the internal surface of the steel cylinder is rusted, and severe self-discharge occurs, so that the storage performance of the battery is rapidly reduced.
Disclosure of Invention
The invention aims to solve the problems of large contact resistance, short storage life, poor anti-seismic performance and the like of the conventional alkaline zinc-manganese battery, and provides a surface treatment method which enables the external surface of the positive current collector of the alkaline zinc-manganese battery to be bright and the internal surface to be corrosion-resistant and has a cog structure.
The purpose of the invention is realized by the following technical scheme:
(1) Chemical oil removal: the steel cylinder is placed in degreasing liquid at 30-80 ℃ for degreasing for 1-2 hours; the deoiling liquid is prepared from the following substances in percentage by weight:
5 to 10 percent of sodium hydroxide
2 to 5 percent of sodium carbonate
5 to 10 percent of sodium phosphate
1 to 5 percent of sodium silicate
1 to 3 percent of OP emulsifier
0.1 to 0.5 percent of sodium dodecyl sulfate
80 to 85 percent of water
Cleaning with water after oil removal;
(2) Micro-etching and polishing: placing the steel cylinder cleaned after oil removal in a vibration polishing machine at room temperature, adding a microetching solution and an acid-resistant abrasive, and polishing for 1-3 hours, wherein the microetching solution comprises the following components in percentage by weight:
1 to 10 percent of inorganic acid
0.1 to 0.5 percent of surfactant
85 to 95 percent of water
The inorganic acid can be hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid; the surfactant can be peregal, TX-10, OP emulsifier, betaine or trimethyl alkyl ammonium bromide; the acid-resistant abrasive material can be conical silicon carbide, the particle size of the acid-resistant abrasive material is larger than the diameter of the steel cylinder, and the acid-resistant abrasive material is cleaned by water and immediately subjected to chemical nickel plating after microetching and polishing;
(3) Chemical nickel plating: the plating solution comprises the following components in percentage by weight:
2 to 3 percent of nickel sulfate,
2 to 3 percent of sodium hypophosphite
1 to 2 percent of sodium acetate,
1.0 to 1.5 percent of sodium citrate,
0.0001 to 0.0002 percent of thiourea,
91 to 93 percent of water,
operating temperature: the pH value is 4 to 5 at 70 to 90 ℃ for 1 to 3 hours; and after chemical nickel plating, cleaning the steel cylinder, washing the steel cylinder by deionized water, and centrifugally drying to obtain the positive current collector with a bright outer surface, a corrosion-resistant inner surface and a cog structure.
Compared with the prior art, the invention has the following advantages: the surface treatment method for the positive current collector with the cog structure on the inner surface of the alkaline zinc-manganese battery has the advantages of simple process and easy operation, the prepared positive current collector with the cog structure has bright and smooth outer surface, rough inner surface micropores and uniform coating thickness of the inner surface and the outer surface, and the alkaline zinc-manganese battery produced by utilizing the positive current collector increases the contact area of a manganese ring and a steel cylinder, so that the combination of the manganese ring and the steel cylinder is firmer, the contact resistance is smaller, and the capacity, the anti-seismic performance and the storage performance of the alkaline zinc-manganese battery can be obviously improved.
Detailed Description
Bottom surface cleaning deviceThe present invention is further specifically described in the following examples, but the embodiments of the present invention are not limited thereto.
| Effect AA battery property Can: comparison group: open circuit Pressing: 1.622V Short circuit electricity Flow: 12.8A Internal resistance: 119.6 omega 1 omega continuous amplification: 52.0min 10 omega is connected Placing: 17.3h 1.8 Ω pulse: 575 times The national standard is as follows: open circuit voltage: 1.50-1.65V 10 Ω discharge: not less than 12h 1.8 Ω pulse: not less than 320 times | The external surface is bright and smooth, and the internal surface is Uniform microhole roughness AA Battery performance: open circuit voltage: 1.623V short-circuit current: 14.5A Internal resistance: 110.1 omega 1 omega continuous amplification: 53.8min 10 omega continuous discharge: 17.5h 1.8 Ω pulse: 586 times | The external surface is bright and smooth, and the internal surface is smooth Uniform surface with rough micropores AA battery performance: open circuit voltage: 1.622V Short-circuit current: 14.8A Internal resistance: 108.5 omega 1 omega continuous amplification: 54.6min 10 omega continuous discharge: 17.4h 1.8 Ω pulse: 593 times | The external surface is bright and smooth, and the internal surface is smooth Uniform surface with rough micropores AA battery performance: open circuit voltage: 1.622V Short-circuit current: 14.6A Internal resistance: 109.2 Ω 1 omega continuous amplification: 54.2min 10 omega continuous discharge: 17.2h 1.8 Ω pulse: 589 times |
Claims (10)
1. A surface treatment method for an alkaline zinc-manganese battery positive current collector with a cog structure on the inner surface is characterized by comprising the following steps: chemical degreasing; (2) micro-etching and polishing; and (3) chemically plating nickel.
2. The surface treatment method for the positive electrode current collector of the alkaline zinc-manganese dioxide battery with the inner surface provided with the cog structure as claimed in claim 1, characterized in that: the chemical oil removal is to place the steel cylinder in oil removal liquid at 30-80 ℃ for oil removal for 1-2 hours, and clean the steel cylinder with water after oil removal.
3. The surface treatment method for the positive electrode current collector of the alkaline zinc-manganese dioxide battery with the inner surface provided with the cog structure as claimed in claim 2, characterized in that: the deoiling liquid is prepared from the following substances in percentage by weight:
5 to 10 percent of sodium hydroxide NaOH
Sodium carbonate Na 2 CO 3 2～5％
Sodium phosphate Na 3 PO 4 ·12H 2 O 5～10％
Sodium silicate Na 2 SiO 3 1～5％
1 to 3 percent of OP emulsifier
0.1 to 0.5 percent of sodium dodecyl sulfate
80 to 85 percent of water
4. The surface treatment method for the positive electrode current collector of the alkaline zinc-manganese dioxide battery with the inner surface provided with the cog structure as claimed in claim 1, is characterized in that: and the microetching polishing is to place the steel cylinder which is cleaned after oil removal in a vibration polishing machine at room temperature, add a microetching solution and an acid-resistant abrasive, perform microetching polishing for 1 to 3 hours, and clean the steel cylinder by water after the microetching polishing.
5. The surface treatment method for the positive electrode current collector of the alkaline zinc-manganese dioxide battery with the inner surface provided with the cog structure as claimed in claim 4, characterized in that: the acid-resistant abrasive is conical silicon carbide, and the particle size of the acid-resistant abrasive is larger than the diameter of the steel cylinder.
6. The surface treatment method for the positive electrode current collector of the alkaline zinc-manganese dioxide battery with the inner surface provided with the cog structure as claimed in claim 4, characterized in that: the microetching liquid comprises the following components in percentage by weight:
1 to 10 percent of inorganic acid
0.1 to 0.5 percent of surfactant
85 to 95 percent of water.
7. The surface treatment method for the positive electrode current collector of the alkaline zinc-manganese dioxide battery with the inner surface provided with the cog structure as claimed in claim 6, characterized in that: the inorganic acid can be one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
8. The surface treatment method for the positive electrode current collector of the alkaline zinc-manganese dioxide battery with the inner surface provided with the cog structure as claimed in claim 6, characterized in that: the surfactant can be any one of peregal, TX-10, OP emulsifier, betaine and trimethyl alkyl ammonium bromide.
9. The surface treatment method for the positive electrode current collector of the alkaline zinc-manganese dioxide battery with the inner surface provided with the cog structure as claimed in claim 1, is characterized in that: the chemical nickel plating solution comprises the following components in percentage by weight:
NiSO nickel sulfate 4 ·7H 2 O 2～3％，
Sodium hypophosphite NaH 2 PO 2 ·H 2 O 2～3％
Sodium acetate NaC 2 H 3 O 2 1～2％，
Sodium citrate Na 3 C 6 H 5 O 7 ·2H 2 O 1.0～1.5％，
0.0001 to 0.0002 percent of thiourea,
91 to 93 percent of water.
10. The surface treatment method for the positive electrode current collector of the alkaline zinc-manganese dioxide battery with the inner surface provided with the cog structure as claimed in claim 1, characterized in that: the operation temperature of the chemical nickel plating is 70-90 ℃, the pH value is 4-5, the time is 1-3 hours, after the chemical nickel plating, the steel cylinder is cleaned and washed by deionized water, and finally, the steel cylinder is centrifugally dried.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02134740 CN1259743C (en) | 2002-09-16 | 2002-09-16 | Surface treatment method for positive current collector of alkaline zinc-manganese battery with inner surface provided with cog structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02134740 CN1259743C (en) | 2002-09-16 | 2002-09-16 | Surface treatment method for positive current collector of alkaline zinc-manganese battery with inner surface provided with cog structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1404175A true CN1404175A (en) | 2003-03-19 |
| CN1259743C CN1259743C (en) | 2006-06-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02134740 Expired - Fee Related CN1259743C (en) | 2002-09-16 | 2002-09-16 | Surface treatment method for positive current collector of alkaline zinc-manganese battery with inner surface provided with cog structure |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102195069A (en) * | 2010-03-03 | 2011-09-21 | 三星Sdi株式会社 | Battery pack and method of manufacturing same |
| CN102758237A (en) * | 2012-07-31 | 2012-10-31 | 厦门建霖工业有限公司 | High-corrosion-resistance surface treatment method of zinc alloy by hexavalent chrome color emulation |
| CN103334095A (en) * | 2012-10-15 | 2013-10-02 | 上海应用技术学院 | A chemical nickel plating solution and applications thereof |
| CN104513986A (en) * | 2014-12-29 | 2015-04-15 | 东莞市凯盟表面处理技术开发有限公司 | Stainless steel normal temperature chemical polishing solution and polishing technology |
-
2002
- 2002-09-16 CN CN 02134740 patent/CN1259743C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102195069A (en) * | 2010-03-03 | 2011-09-21 | 三星Sdi株式会社 | Battery pack and method of manufacturing same |
| CN102758237A (en) * | 2012-07-31 | 2012-10-31 | 厦门建霖工业有限公司 | High-corrosion-resistance surface treatment method of zinc alloy by hexavalent chrome color emulation |
| CN102758237B (en) * | 2012-07-31 | 2015-01-28 | 厦门建霖工业有限公司 | High-corrosion-resistance surface treatment method of zinc alloy by hexavalent chrome color emulation |
| CN103334095A (en) * | 2012-10-15 | 2013-10-02 | 上海应用技术学院 | A chemical nickel plating solution and applications thereof |
| CN103334095B (en) * | 2012-10-15 | 2016-07-20 | 上海应用技术学院 | A kind of chemical nickel-plating liquid and application thereof |
| CN104513986A (en) * | 2014-12-29 | 2015-04-15 | 东莞市凯盟表面处理技术开发有限公司 | Stainless steel normal temperature chemical polishing solution and polishing technology |
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| Publication number | Publication date |
|---|---|
| CN1259743C (en) | 2006-06-14 |
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Granted publication date: 20060614 Termination date: 20120916 |