CN103194743A - Surface treatment method of nickel metal strip for lithium-ion battery negative electrode ear - Google Patents
Surface treatment method of nickel metal strip for lithium-ion battery negative electrode ear Download PDFInfo
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- CN103194743A CN103194743A CN201310080486XA CN201310080486A CN103194743A CN 103194743 A CN103194743 A CN 103194743A CN 201310080486X A CN201310080486X A CN 201310080486XA CN 201310080486 A CN201310080486 A CN 201310080486A CN 103194743 A CN103194743 A CN 103194743A
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The present invention discloses a surface treatment method of a nickel metal strip for a lithium-ion battery negative electrode ear. The method includes two steps. A treatment liquid in a first step includes at least a hexavalent chromium compound, a fluorine compound, and a phosphorus compound. A treatment liquid in a second step includes at least organic acid, inorganic acid, and a fluorine compound. A chemical conversion film is formed by heating and drying after applying the treatment liquid on the surface of the nickel metal strip. The nickel metal strip treated by the method of the present invention after hot pressing with an ear adhesive has excellent electrolyte resistance property. The nickel metal strip is directly immersed in the electrolyte at 85 DEG C for 4.5 hours. The bonding strength is almost unchanged. Meanwhile, the nickel metal strip after treatment still has good soldering properties, and can be directly soldered on the surface thereof. The metal nickel strip is used for the production of lithium ion battery ears. The production process can be simplified. The cost is reduced.
Description
Technical field
The present invention relates to the surface treatment of lithium ion battery nickel metal strip, metallic nickel bar after the processing not only has good tin-welding, and with lug glue heat pressure adhesive after have splendid electrolyte resistance performance, can be used for producing the negative lug of lithium ion battery, particularly polymer Li-ion battery.
Background technology
Lithium ion battery is a kind of rechargeable cell, because its operating voltage height, have extended cycle life, advantage such as specific energy height, memory-less effect, self-discharge are little, be widely used in electronics such as digital product such as mobile phone, notebook computer, pick up camera and new energy electric motor vehicle and the device.
Polymer Li-ion battery replaces liquid electrolyte with solid polymer electrolyte, and this polymkeric substance can be " dry state ", also can be " colloidal state ", at present most of colloidal state polymer ionogen that adopts.Compare with liquid lithium ionic cell, polymer Li-ion battery is safer, because the possibility of electrolyte leakage is littler, and polymer Li-ion battery can accomplish forr a short time, thinner, and can be made into the battery of arbitrary shape.Therefore, the market requirement of polymer Li-ion battery is always in sustainable growth.
The nickel lug is to be used for metallic conductor that negative pole is extracted from electric core in the polymer Li-ion battery, requires to have good electrolyte resistance and tin-welding.Yet existing polymer Li-ion battery nickel lug tin-welding is undesirable, makes the manufacturing process of battery become complicated.Common way is before carrying out soldering, polishes in soldering place with sand paper earlier, and this not only increases operation, reduces production efficiency, and causes cost to rise.Chinese patent (application number is 200910190249.2) discloses a kind of polymer battery lug and surface treatment method thereof, it adopts ammonium bifluoride, chromic oxide, boric acid, sodium phosphate that lug is handled, the electrolyte resistance of gained lug is good, but the problem of tin-welding difference does not still solve.
In sum, be badly in need of a kind of new nickel metal surface treatment technology, when improving its electrolyte resistance performance, keep the tin-welding of nickel constant, in order to directly carry out soldering on its surface.
Summary of the invention
The object of the present invention is to provide a kind of new nickel metal surface treating method, the metallic nickel bar of handling through this method not only has good electrolyte resistance performance, but and has a good tin-welding, can directly carry out soldering on its surface, to be used for the production of polymer Li-ion battery negative lug.
The present invention is achieved by the following technical solutions:
A kind of surface treatment method of the nickel metal strip for lithium ionic cell cathode ear pole is characterized in that described surface treatment method may further comprise the steps:
1), preparation the first step treatment solution, the first step treatment solution is solvent with water or deionized water, contains at least in every liter for the treatment of solution:
Hexavalent chromium compound 0.5～30g/l
Phosphorus compound 10～60g/l
Fluorine cpd 0.5～20g/l,
Described hexavalent chromium compound is to be selected from chromic oxide, chromium chloride, lithium chromate, Sodium chromate, potassium bichromate, the sodium dichromate 99 one or more,
Described phosphorus compound is to be selected from phosphoric acid, polyphosphoric acid, tetra-sodium and the salt compounds thereof one or more,
Described fluorine cpd are to be selected from Sodium Fluoride, Neutral ammonium fluoride, Potassium monofluoride, hydrofluoric acid, fluoroboric acid, the sodium hydrogen fluoride one or more;
2), the first step treatment solution be heated to 30～70 ℃ be applied in the nickel bar surface, the treatment time is 2～10min;
3), the preparation second the step treatment solution, second the step treatment solution be solvent with water or deionized water, contain at least in every liter for the treatment of solution:
Organic acid 5～40g/l
Fluorine cpd 0.5～20g/l
Mineral acid 5～40g/l
Described organic acid is to be selected from oxalic acid, citric acid, vinylformic acid, Succinic Acid, tartrate, the oxysuccinic acid one or more,
Described fluorine cpd are to be selected from Sodium Fluoride, Neutral ammonium fluoride, Potassium monofluoride, hydrofluoric acid, fluoroboric acid, the sodium hydrogen fluoride one or more,
Described mineral acid is to be selected from nitric acid, hydrofluoric acid, phosphoric acid, boric acid, hydrochloric acid, the sulfuric acid one or more,
4), will be through step 2) after the nickel metal strip water handled cleans, the second step treatment solution is heated to 40～80 ℃ is applied in the nickel bar surface, the treatment time is 2～10min;
5), with the nickel metal strip through 60～150 ℃ of heat dryings, form the chemical conversion rete.
The nickel purity of above-mentioned nickel metal strip is more than 99.5%, and thickness is 0.02～0.2mm.
The salt of described phosphoric acid, polyphosphoric acid, tetra-sodium is one or more in primary ammonium phosphate, potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC, zinc phosphate, triammonium phosphate, tertiary sodium phosphate, Tripotassium phosphate, trisodium phosphate, potassium pyrophosphate, the Sodium Acid Pyrophosphate.
The described application process that treatment solution is applied in the nickel bar surface is: be coated with a kind of in method, spin-coating method, the spraying method by immersion method, rod treatment solution is coated on the nickel bar surface.
Nickel of the present invention forms one deck chemical conversion rete on the surface after surface treatment, this stratification transforms rete with firm the adhering to each other and employed gel electrolyte and gel electrolyte hydrofluoric acid rotten or that hydrolysis produces are had erosion resistance of nickel and lug glue, can make nickel keep good tin-welding.
The chemical conversion rete of described nickel surface can easily be realized, for example, use the water treatment liquid that contains hexavalent chromium compound, fluorine cpd, phosphorus compound at nickel surface, after water cleans, use the water treatment liquid that contains organic acid, fluorine cpd, mineral acid again, clean the post-heating drying through water
Beneficial effect
The present invention is for the preparation of the negative lug of polymer Li-ion battery, the nickel metal strip that process the technology of the present invention was handled, with the yellow glue of Japanese DNP, clear and black glue through behind the heat pressure adhesive, has good electrolyte resistance performance, directly soaked 4.5 hours through 85 ℃ of electrolytic solution, cohesive strength is constant substantially, the permanent stopping property in subsequent storage and use of the battery after can guaranteeing to encapsulate, the security that has improved battery and consumer thereof.
Nickel metal strip through the technology of the present invention was handled not only has good electrolyte resistance performance but also has good soldering performance, can directly carry out soldering on its surface, has simplified the manufacturing process of lug, and can reduce production costs.
Embodiment
The composition that contains in the treatment solution is as follows:
Composition (A) hexavalent chromium compound
A-1: chromium trioxide
A-2: Sodium chromate
A-3: sodium dichromate 99
Composition (B) phosphorus compound
B-1: phosphoric acid
B-2: trisodium phosphate
Composition (C) fluorine cpd
C-1: Sodium Fluoride
C-2: Potassium monofluoride
Composition (D) organic acid
D-1: oxalic acid
D-2: citric acid
D-3: vinylformic acid
Composition (E) mineral acid
E-1: hydrochloric acid
E-2: nitric acid
The first step treatment solution: in every premium on currency, mix preparation aqueous treatment agent a to e according to the amount (mol) of every kind of mentioned component shown in the table one.
Table one
Unit: mol
The second step treatment solution: in every premium on currency, mix preparation aqueous treatment agent f to j according to the amount (mol) of every kind of mentioned component shown in the table two.
Table two
Unit: mol
Embodiment 1
The preparation for the treatment of solution: water or deionized water are solvent, and the first step treatment solution is a, and the second step treatment solution is f;
Treatment process:
(1) removes nickel bar surface grease, clean up with tap water;
(2) will immerse 6min in 40 ℃ the first step treatment solution through the nickel bar that handle (1), clean up with tap water;
(3) will immerse 8min in 40 ℃ the second step treatment solution through the nickel bar that handle (2), clean up with tap water;
(4) the nickel bar that will handle through (3) is through 80 ℃ of heat dryings.
Embodiment 2
The preparation for the treatment of solution: the first step treatment solution is b, and the second step treatment solution is g;
Treatment process:
(1) removes nickel bar surface grease, clean up with tap water;
(2) will immerse 6min in 40 ℃ the first step treatment solution through the nickel bar that handle (1), clean up with tap water;
(3) will immerse 8min in 40 ℃ the second step treatment solution through the nickel bar that handle (2), clean up with tap water;
(4) the nickel bar that will handle through (3) is through 80 ℃ of heat dryings.
Embodiment 3
The preparation for the treatment of solution: the first step treatment solution is c, and the second step treatment solution is h;
Treatment process:
(1) the surface nickel bar cleans up with tap water except degrease;
(2) will immerse 6min in 40 ℃ the first step treatment solution through the nickel bar that handle (1), clean up with tap water;
(3) will immerse 8min in 40 ℃ the second step treatment solution through the nickel bar that handle (2), clean up with tap water;
(4) the nickel bar that will handle through (3) is through 80 ℃ of heat dryings.
Embodiment 4
The preparation for the treatment of solution: the first step treatment solution is d, and the second step treatment solution is i;
Treatment process:
(1) removes nickel bar surface grease, clean up with tap water;
(2) will in the first step treatment solution of nickel bar at 40 ℃ of (1) processing, handle 6min by spray, clean up with tap water;
(3) will in the second step treatment solution of nickel bar at 40 ℃ of (2) processing, handle 8min by spray, clean up with tap water;
(4) the nickel bar that will handle through (3) is through 80 ℃ of heat dryings.
Embodiment 5
The preparation for the treatment of solution: the first step treatment solution is e, and the second step treatment solution is j;
Treatment process:
(1) removes nickel bar surface grease, clean up with tap water;
(2) will in the first step treatment solution of nickel bar at 40 ℃ of (1) processing, handle 6min by spray, clean up with tap water;
(3) will in the second step treatment solution of nickel bar at 40 ℃ of (2) processing, handle 8min by spray, clean up with tap water;
(4) the nickel bar that will handle through (3) is through 80 ℃ of heat dryings.
Above-mentioned treated nickel metal strip for the preparation of producing lithium ionic cell cathode ear pole, behind treated nickel metal strip and the lug glue heat pressure adhesive, is directly soaked with electrolytic solution, and 85 ℃ of its cohesive strengths in following 4.5 hours are almost constant; Simultaneously, the nickel metal strip after the processing still has good soldering performance, can directly carry out soldering on its surface, and after the soldering, metallic tin can be tiled in nickel bar surface.This metallic nickel bar is used for the production of lithium ion cell polar ear, can simplify production technique, and reduce cost.
Claims (4)
1. surface treatment method that is used for the nickel metal strip of lithium ionic cell cathode ear pole is characterized in that described surface treatment method may further comprise the steps:
1), preparation the first step treatment solution, the first step treatment solution is solvent with water or deionized water, contains at least in every liter for the treatment of solution:
Hexavalent chromium compound 0.5～30g/l
Phosphorus compound 10～60g/l
Fluorine cpd 0.5～20g/l,
Described hexavalent chromium compound is to be selected from chromic oxide, chromium chloride, lithium chromate, Sodium chromate, potassium bichromate, the sodium dichromate 99 one or more, described phosphorus compound is to be selected from phosphoric acid, polyphosphoric acid, tetra-sodium and the salt thereof one or more, and described fluorine cpd are to be selected from Sodium Fluoride, Neutral ammonium fluoride, Potassium monofluoride, hydrofluoric acid, fluoroboric acid, the sodium hydrogen fluoride one or more;
2), the first step treatment solution be heated to 30～70 ℃ be applied in the nickel bar surface, the treatment time is 2～10min;
3), the preparation second the step treatment solution, second the step treatment solution be solvent with water or deionized water, contain at least in every liter for the treatment of solution:
Organic acid 5～40g/l
Fluorine cpd 0.5～20g/l
Mineral acid 5～40g/l
Described organic acid is to be selected from oxalic acid, citric acid, vinylformic acid, Succinic Acid, tartrate, the oxysuccinic acid one or more,
Described fluorine cpd are to be selected from Sodium Fluoride, Neutral ammonium fluoride, Potassium monofluoride, hydrofluoric acid, fluoroboric acid, the sodium hydrogen fluoride one or more,
Described mineral acid is to be selected from nitric acid, hydrofluoric acid, phosphoric acid, boric acid, hydrochloric acid, the sulfuric acid one or more,
4), will be through step 2) after the nickel metal strip water handled cleans, the second step treatment solution is heated to 40～80 ℃ is applied in the nickel bar surface, the treatment time is 2～10min;
5), with the nickel metal strip through 60～150 ℃ of heat dryings, form the chemical conversion rete.
2. the surface treatment method of the nickel metal strip for lithium ionic cell cathode ear pole as claimed in claim 1, it is characterized in that the salt of described phosphoric acid, polyphosphoric acid, tetra-sodium is one or more in primary ammonium phosphate, potassium primary phosphate, SODIUM PHOSPHATE, MONOBASIC, zinc phosphate, triammonium phosphate, tertiary sodium phosphate, Tripotassium phosphate, trisodium phosphate, potassium pyrophosphate, the Sodium Acid Pyrophosphate.
3. the surface treatment method of the nickel metal strip for lithium ionic cell cathode ear pole as claimed in claim 1, it is characterized in that the described application process that treatment solution is applied in the nickel bar surface is: be coated with a kind of in method, spin-coating method, the spraying method by immersion method, rod treatment solution is coated on the nickel bar surface.
4. the surface treatment method of the nickel metal strip for lithium ionic cell cathode ear pole as claimed in claim 1 is characterized in that the nickel purity of described nickel metal strip is greater than 99.5%, and thickness is 0.02～0.2mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310080486.XA CN103194743B (en) | 2013-03-13 | 2013-03-13 | Surface treatment method of nickel metal strip for lithium-ion battery negative electrode ear |
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| CN201310080486.XA CN103194743B (en) | 2013-03-13 | 2013-03-13 | Surface treatment method of nickel metal strip for lithium-ion battery negative electrode ear |
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| CN103194743B CN103194743B (en) | 2014-12-24 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105702907A (en) * | 2016-04-06 | 2016-06-22 | 东莞市安德丰电池有限公司 | Yellow glue for soft-packaging lithium battery and application method thereof |
| CN108930043A (en) * | 2018-08-15 | 2018-12-04 | 东莞市同盛电子科技有限公司 | A kind of cleaning agent and preparation method thereof removing metal oxide layer and application method |
| CN109967437A (en) * | 2018-11-26 | 2019-07-05 | 深圳市德惠电池材料有限公司 | A kind of easy welding electrode connection sheet blank treatment process |
| CN111235560A (en) * | 2020-03-20 | 2020-06-05 | 无锡雷德环保设备有限公司 | Process for passivating hexavalent chromium of phosphorus chemical nickel coating in new energy automobile electrode material |
| CN115042483A (en) * | 2022-05-30 | 2022-09-13 | 广东维都利新能源有限公司 | Multi-metal bonding mechanism with corrosion resistance and bonding method thereof |
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| US2868682A (en) * | 1957-01-31 | 1959-01-13 | Parker Rust Proof Co | Chromate-fluoride type coating solutions and method of treating metal surfaces therewith |
| JPS6187878A (en) * | 1984-10-03 | 1986-05-06 | Nippon Light Metal Co Ltd | Formation of corrosion resistant hydrophilic film |
| CN101667632A (en) * | 2009-09-25 | 2010-03-10 | 深圳世纪新能源电池有限公司 | Polymer battery lug and surface processing method thereof |
| CN102376984A (en) * | 2010-08-25 | 2012-03-14 | 惠州泰科立集团股份有限公司 | Ultrathin rechargeable battery and manufacturing process thereof |
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2013
- 2013-03-13 CN CN201310080486.XA patent/CN103194743B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2868682A (en) * | 1957-01-31 | 1959-01-13 | Parker Rust Proof Co | Chromate-fluoride type coating solutions and method of treating metal surfaces therewith |
| JPS6187878A (en) * | 1984-10-03 | 1986-05-06 | Nippon Light Metal Co Ltd | Formation of corrosion resistant hydrophilic film |
| CN101667632A (en) * | 2009-09-25 | 2010-03-10 | 深圳世纪新能源电池有限公司 | Polymer battery lug and surface processing method thereof |
| CN102376984A (en) * | 2010-08-25 | 2012-03-14 | 惠州泰科立集团股份有限公司 | Ultrathin rechargeable battery and manufacturing process thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105702907A (en) * | 2016-04-06 | 2016-06-22 | 东莞市安德丰电池有限公司 | Yellow glue for soft-packaging lithium battery and application method thereof |
| CN105702907B (en) * | 2016-04-06 | 2018-01-30 | 东莞市安德丰电池有限公司 | A kind of soft package lithium battery yellow glue and application method |
| CN108930043A (en) * | 2018-08-15 | 2018-12-04 | 东莞市同盛电子科技有限公司 | A kind of cleaning agent and preparation method thereof removing metal oxide layer and application method |
| CN109967437A (en) * | 2018-11-26 | 2019-07-05 | 深圳市德惠电池材料有限公司 | A kind of easy welding electrode connection sheet blank treatment process |
| CN111235560A (en) * | 2020-03-20 | 2020-06-05 | 无锡雷德环保设备有限公司 | Process for passivating hexavalent chromium of phosphorus chemical nickel coating in new energy automobile electrode material |
| CN115042483A (en) * | 2022-05-30 | 2022-09-13 | 广东维都利新能源有限公司 | Multi-metal bonding mechanism with corrosion resistance and bonding method thereof |
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| CN103194743B (en) | 2014-12-24 |
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