CN101899695B - Method for preparing nickel-plated aluminum tab by two-step electroplating - Google Patents

Method for preparing nickel-plated aluminum tab by two-step electroplating Download PDF

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Publication number
CN101899695B
CN101899695B CN2010102417158A CN201010241715A CN101899695B CN 101899695 B CN101899695 B CN 101899695B CN 2010102417158 A CN2010102417158 A CN 2010102417158A CN 201010241715 A CN201010241715 A CN 201010241715A CN 101899695 B CN101899695 B CN 101899695B
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China
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nickel
plated aluminum
nickel plating
aluminium flake
large stretch
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CN101899695A (en
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童庆松
杜洪彦
黄行康
郑华杰
林燕燕
陈梅蓉
曾宝珊
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Fujian Normal University
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Fujian Normal University
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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

Abstract

The invention relates to a method for preparing a nickel-plated aluminum tab by two-step electroplating, which is characterized by comprising the following steps of: preparing a large nickel-plated aluminum sheet; and then cutting the large nickel-plated aluminum sheet into the nickel-plated aluminum tab. Current waveform of the two-step electroplating is one of an asymmetric square wave, an asymmetric sine wave, an asymmetric cosine wave, an asymmetric triangular wave or impulse wave, or a combined current waveform formed by two of the above-mentioned current waveforms. When the prepared large nickel-plated aluminum sheet is cut into the nickel-plated aluminum tab, the area of the large nickel-plated aluminum sheet is 3 to 10,000 times that of the nickel-plated aluminum tab, and the width of the nickel-plated aluminum tab may be of any dimension ranging from 1 to 200 millimeters. The nickel-plated aluminum tab is used as a battery anode current collector, so that the preparation procedures for the prepared battery can be reduced and the battery has the remarkable advantages of safety, reliability and the like.

Description

A kind of method of preparing nickel-plated aluminum tab by two-step electroplating
Technical field
The invention belongs to technical field of battery manufacture, relate to the preparation method of the lug of the lug of a kind of lithium cell and lithium ion battery, particularly polymer Li-ion battery, flexible packing lithium ion battery and duricrust lithium ion battery.
Background technology
Aluminium and duraluminum have that density is little, ductility and good toughness, be easy to premium properties such as processing, extensively as the lug of lug, particularly polymer Li-ion battery, flexible packing lithium ion battery and the duricrust lithium ion battery of lithium cell and lithium ion battery.Yet, the own corrosion-vulnerable of aluminium and duraluminum, big, the welding difficulty of not wear-resisting, contact resistance.And the nickel metallic surface can generate passive film as thin as a wafer rapidly, than aluminium pole ears better opposing corrosive power is arranged.Therefore, adopt modes such as riveted joint, ultrasonic spot welding or LBW more, on the aluminium pole ears that battery uses, connect nickel lug (promptly changeing nickel), the other end with the nickel lug is welded on the IC circuit card again.Like this, anode pole piece exists between the IC circuit card " aluminium-aluminium ", " aluminium-nickel ", " nickel-copper " several tie points (or solder joint).Because this connection belongs to a connection; Tie point (or solder joint) area is little; Exist to connect that (or welding) is not firm, virtual connections (or rosin joint), tie point (or solder joint) contact resistance are big, tie point (or solder joint) is prone to problems such as oxidized when depositing, there are problems such as batch unstable properties in the battery of preparation.During battery discharge, particularly during heavy-current discharge, tie point (or solder joint) weld possibly produce too much problems such as heat because of resistance is excessive, the battery ability of externally doing work is obviously weakened, the safety issue that also causes battery to use.In when charging, possibly cause potential safety hazards such as heating that charging difficulty and charging cause, burning because of tie point (or solder joint) sealing-off and welding resistance are excessive.In addition, change the nickel process and increased the step of cell preparation, thereby increased battery cost.
In order to overcome above deficiency, the invention provides a kind of method that obtains nickel-plated aluminum lug through the large stretch of nickel plating aluminium flake of preparation.This nickel-plated aluminum lug can be extensively as the lug of lithium cell and lithium ion battery, particularly as the lug of polymer Li-ion battery, flexible packing lithium ion battery and duricrust lithium ion battery.When nickel-plated aluminum lug of the present invention during as the lug of lithium cell and lithium ion battery; Anode pole piece has only between the IC circuit card " aluminium-aluminium ", " nickel-copper " tie point; And connect face connection or the body connection that changes " aluminium-nickel plating alloy " into putting between original " aluminium-nickel "; Obviously reduce contact resistance, improved the durability of connecting zone, improved the consistence of battery batch performance.The charge-discharge performance of battery, particularly high rate during charging-discharging have been improved.
Utility model patent ZL2008202125092 relates to a kind of lithium cell aluminium pole ears, comprises banded aluminum strip, at an end of aluminum strip chemical Ni-plating layer is arranged.But, this patent does not relate to the concrete preparation method of nickel-plated aluminum lug and complete structure formation.Though existing many papers and patent relate to the method for nickel plating on the aluminium; The method that relates to a kind of nickel plating on siliceous aluminum steel, sheet, rod like patent ZL 018091091; Patent ZL981149332 relate to a kind of on steel substrate the method for electroplating of low-stress nickel, patent CN101245480 relates to a kind of method at carbon, iron, copper electroplating nickel on surface.But, these patents all do not relate to a kind of method that is suitable as the nickel plating of battery aluminium pole ears.Since the nickel-plated aluminum lug that is used for lithium (ion) battery to the requirement of nickeling layer and common nickel plating aluminium flake to coating require differently, wherein, in the emphasis consideration nickel-plated aluminum lug contact resistance, resistance to bend(ing) ability between the nickeling layer and aluminium flake.Factors such as heat dispersion, electrolyte resistance corrosive nature are for the luminance brightness of nickel plating aluminium flake and be indifferent to.
Summary of the invention
The present invention prepares large stretch of nickel plating aluminium flake earlier, more large stretch of nickel plating aluminium flake is cut to nickel-plated aluminum lug.Preparing large stretch of nickel plating aluminium flake is made up of following two step plating step:
The solution formula of two galvanized the first step nickel plating of step is in 1000ml: NiSO 46H 2O 240g～300g, NiCl 26H 2O 2g～20g, H 3BO 335g～55g, MgSO 47H 2O 30g～50g, tensio-active agent 0.01g～13.5g.
50 ℃～70 ℃ of bath temperatures, plating bath pH 3.1～5.5.
Described tensio-active agent is meant sodium lauryl sulphate, X 2073 or the TX10 of concentration in 0.1g/L～13.5g/L scope, or concentration is at Triple Pressed Stearic Acid, trimethyl-glycine or the polysorbate of 0.01g/L～2.0g/L scope.
The solution formula of the galvanized second step nickel plating of two steps is in 1000ml: NiSO 46H 2O 200g～400g, NiCl 26H 2O 20g～100g, H 3BO 320g～50g, sodium lauryl sulphate 0.01g～13.5g, elementary brightening agent 0.1g～5g, second-class brightener 0.05g～2g.
45 ℃～75 ℃ of bath temperatures, pH 3.2～5.2.
Described elementary brightening agent is asccharin, benzene sulfinic acid sodium salt, para toluene sulfonamide or unsaturated fatty acids; Described second-class brightener is butynediol, propiolic alcohol or tonka bean camphor, or the reaction product of butynediol and oxyethane, or the reaction product of butynediol and epoxy chloropropane.
Above-mentioned galvanized current waveform of two steps is asymmetrical square wave, asymmetric sine wave, asymmetric CW, asymmetric choppy sea or pulse wave, or a kind of current waveform of being combined into of above-mentioned two kinds of current waveforms; Power frequency is 0.1Hz～10000Hz, and dutycycle is 1/100～10000/100, and current density is 0.01A/dm 2～2.5A/dm 2, electroplating time is 0.1 second～35 minutes.
When the large stretch of nickel plating aluminium flake for preparing was cut to nickel-plated aluminum lug, the area of large stretch of nickel plating aluminium flake was 3 times to 10000 times of nickel-plated aluminum lug, and the width of nickel-plated aluminum lug is any width between 1 millimeter to 200 millimeters.Here specify the size of nickel-plated aluminum lug to satisfy following relation: length＞width＞thickness.
Embodiment
Below in conjunction with embodiment the present invention is further specified.Embodiment further replenishes and explanation of the present invention, rather than to the restriction of patent of the present invention.
Embodiment 1
Present embodiment is the large stretch of nickel plating aluminium flake of preparation earlier, more large stretch of nickel plating aluminium flake is cut to nickel-plated aluminum lug.Preparing large stretch of nickel plating aluminium flake is made up of following two step plating step:
The first step nickel plating solution is following in the prescription of 1000ml: NiSO 46H 2O 240g, NiCl 26H 2O 2g, H 3BO 335g, MgSO 47H 2O 30g, sodium lauryl sulphate 0.1g, 50 ℃ of bath temperatures, plating bath pH 3.1.
The galvanized current waveform of the first step is an asymmetrical square wave, and power frequency is 0.1Hz, and dutycycle is 1/100, and current density is 0.01A/dm 2, electroplating time is 0.1 second.
The solution of the second step nickel plating is following in the prescription of 1000ml: NiSO 46H 2O 200g, NiCl 26H 2O20g, H 3BO 320g, sodium lauryl sulphate 0.01g, benzene sulfinic acid sodium salt 0.1g, propiolic alcohol 0.05g.
45 ℃ of bath temperatures, pH 3.2.
The second step nickel plating current waveform can be asymmetrical square wave, and power frequency is 0.1Hz, and dutycycle is 1/100, and current density is 0.01A/dm 2, electroplating time is 0.1 second.
When the large stretch of nickel plating aluminium flake for preparing was cut to nickel-plated aluminum lug, the area of large stretch of nickel plating aluminium flake was 3 times of nickel-plated aluminum lug, and the width of nickel-plated aluminum lug is 1 millimeter.
Embodiment 2
Present embodiment is the large stretch of nickel plating aluminium flake of preparation earlier, more large stretch of nickel plating aluminium flake is cut to nickel-plated aluminum lug.Preparing large stretch of nickel plating aluminium flake is made up of following two step plating step:
The first step nickel plating solution is following in the prescription of 1000ml: NiSO 46H 2O 240g, NiCl 26H 2O2g, H 3BO 335g, MgSO 47H 2O 30g, X 2073 13.5g, 50 ℃ of bath temperatures, plating bath pH 3.1
The current waveform of the first step nickel plating is asymmetric sine wave, and power frequency is 0.1Hz, and dutycycle is 1/100, and current density is 0.01A/dm 2, electroplating time is 0.1 second.
The second step nickel plating solution is following in the prescription of 1000ml: NiSO 46H 2O 400g, NiCl 26H 2O10g,, H 3BO 350g, sodium lauryl sulphate 13.5g, para toluene sulfonamide 5g, tonka bean camphor 0.2g.
75 ℃ of bath temperatures, plating bath pH5.2.
The second step nickel plating current waveform is asymmetric choppy sea, and power frequency is 10000Hz, and dutycycle is 10000/100, and current density is 2.5A/dm 2, electroplating time is 35 minutes.
When the large stretch of nickel plating aluminium flake for preparing was cut to nickel-plated aluminum lug, the area of large stretch of nickel plating aluminium flake was 3000 times of nickel-plated aluminum lug, and the width of nickel-plated aluminum lug is 10 millimeters.
Embodiment 3
Present embodiment is the large stretch of nickel plating aluminium flake of preparation earlier, more large stretch of nickel plating aluminium flake is cut to nickel-plated aluminum lug.Preparing large stretch of nickel plating aluminium flake is made up of following two step plating step:
The first step nickel plating solution is following in the prescription of 1000ml: NiSO 46H 2O 300g, NiCl 26H 2O 20g, H 3BO 355g, MgSO 47H 2O 50g, TX10 3g.
70 ℃ of bath temperatures, plating bath pH5.5
The current waveform of the first step nickel plating is asymmetric choppy sea, and power frequency is 10000Hz, and dutycycle is 10000/100, and current density is 2.5A/dm 2, electroplating time is 35 minutes.
The solution of the second step nickel plating is following in the prescription of 1000ml: NiSO 46H 2O 400g, NiCl 26H 2O100g, H 3BO 350g, sodium lauryl sulphate 3g, asccharin 5g, tonka bean camphor 2g.
75 ℃ of bath temperatures, pH 5.2.
The current waveform of the second step nickel plating is a pulse wave, and power frequency is 10000Hz, and dutycycle is 10000/100, and current density is 2.5A/dm 2, electroplating time is 35 minutes.
When the large stretch of nickel plating aluminium flake for preparing was cut to nickel-plated aluminum lug, the area of large stretch of nickel plating aluminium flake was 300 times of nickel-plated aluminum lug, and the width of nickel-plated aluminum lug is 100 millimeters.
Embodiment 4
Present embodiment is the large stretch of nickel plating aluminium flake of preparation earlier, more large stretch of nickel plating aluminium flake is cut to nickel-plated aluminum lug.Preparing large stretch of nickel plating aluminium flake is made up of following two step plating step:
The first step nickel plating solution is following in the prescription of 1000ml: NiSO 46H 2O 300g, NiCl 26H 2O20g, H 3BO 355g, MgSO 47H 2O 50g, Triple Pressed Stearic Acid 0.01g.
Bath temperature is 70 ℃ during plating, plating bath pH 5.5.
The current waveform of the first step nickel plating is an asymmetrical square wave, and power frequency is 10000Hz, and dutycycle is 10000/100, and current density is 2.5A/dm 2, electroplating time is 35 minutes.
The second step nickel plating solution is following in the prescription of 1000ml: NiSO 46H 2O 200g, NiCl 26H 2O 15g, H 3BO 320g, sodium lauryl sulphate 0.01g, benzene sulfinic acid sodium salt 0.1g, butynediol 0.05g.
45 ℃ of bath temperatures, pH 3.2.
The current waveform of the second step nickel plating is the asymmetry pulse ripple, and power frequency is 0.1Hz, and dutycycle is 1/100, and current density is 0.01A/dm 2, electroplating time is 0.1 second.
When the large stretch of nickel plating aluminium flake for preparing was cut to nickel-plated aluminum lug, the area of large stretch of nickel plating aluminium flake was 10000 times of nickel-plated aluminum lug, and the width of nickel-plated aluminum lug is 1 millimeter.
Embodiment 5
Present embodiment is the large stretch of nickel plating aluminium flake of preparation earlier, more large stretch of nickel plating aluminium flake is cut to nickel-plated aluminum lug.Preparing large stretch of nickel plating aluminium flake is made up of following two step plating step:
The first step nickel plating solution is following in the prescription of 1000ml: NiSO 46H 2O 270g, NiCl 26H 2O12g, H 3BO 345g, MgSO 47H 2O 40g, X 2073 0.5g.
60 ℃ of bath temperatures, plating bath pH 4.6.
The current waveform of the first step nickel plating is that asymmetrical square wave and pulse wave are combined into a kind of current waveform, and power frequency is 1000Hz, and dutycycle is 50/100, and current density is 1.5A/dm 2, electroplating time is 15 minutes.
The second step nickel plating solution is following in the prescription of 1000ml: NiSO 46H 2O 300g, NiCl 26H 2O 60g, H 3BO 350g, sodium lauryl sulphate 2.8g, para toluene sulfonamide 4.5g, propiolic alcohol 1.5g.
70 ℃ of bath temperatures, pH 5.1.
The current waveform of the second step nickel plating is an asymmetrical square wave, and power frequency is 5000Hz, and dutycycle is 10000/100, and current density is 1.1A/dm 2, electroplating time is 5 minutes.
When the large stretch of nickel plating aluminium flake for preparing was cut to nickel-plated aluminum lug, the area of large stretch of nickel plating aluminium flake was 10 times of nickel-plated aluminum lug, and the width of nickel-plated aluminum lug is 10 millimeters.
Embodiment 6
Present embodiment is the large stretch of nickel plating aluminium flake of preparation earlier, more large stretch of nickel plating aluminium flake is cut to nickel-plated aluminum lug.Preparing large stretch of nickel plating aluminium flake is made up of following two step plating step:
The first step nickel plating solution is following in the prescription of 1000ml: NiSO 46H 2O 240g, NiCl 26H 2O2g, H 3BO 335g, MgSO 47H 2O 30g, trimethyl-glycine 2.0g.
50 ℃ of bath temperatures, plating bath pH 3.1.
The galvanized current waveform of the first step is a pulse wave, and power frequency is 10000Hz, and dutycycle is 10/100, and current density is 0.1A/dm 2, electroplating time is 100 seconds.
The second step nickel plating solution is following in the prescription of 1000ml: NiSO 46H 2O 200g, NiCl 26H 2O 20g, H 3BO 320g, sodium lauryl sulphate 0.01g, benzene sulfinic acid sodium salt 0.1g, butynediol 2g.
75 ℃ of bath temperatures, pH 5.2.
The current waveform of the second step nickel plating is asymmetric choppy sea, and power frequency is 10000Hz, and dutycycle is 1/100, and current density is 2.1A/dm 2, electroplating time is 30 seconds.
When the large stretch of nickel plating aluminium flake for preparing was cut to nickel-plated aluminum lug, the area of large stretch of nickel plating aluminium flake was 10000 times of nickel-plated aluminum lug, and the width of nickel-plated aluminum lug is 1 millimeter.
Embodiment 7
Present embodiment is the large stretch of nickel plating aluminium flake of preparation earlier, more large stretch of nickel plating aluminium flake is cut to nickel-plated aluminum lug.Preparing large stretch of nickel plating aluminium flake is made up of following two step plating step:
The first step nickel plating solution is following in the prescription of 1000ml: NiSO 46H 2O 240g, NiCl 26H 2O 2g, H 3BO 335g, MgSO 47H 2O 30g, polysorbate 0.01g.
Bath temperature is 50 ℃ during plating, plating bath pH 5.5.
The current waveform of the first step nickel plating is asymmetric sine wave, and power frequency is 500Hz, and dutycycle is 1/100, and current density is 0.01A/dm 2, electroplating time is 20 minutes.
The second step nickel plating solution is following in the prescription of 1000ml: NiSO 46H 2O 400g, NiCl 26H 2O20g, H 3BO 320g, sodium lauryl sulphate 0.5g, benzene sulfinic acid sodium salt 1g, tonka bean camphor 2g.
75 ℃ of electroplating bath solution temperature, pH 5.2.
The current waveform of the second step nickel plating is asymmetric sine wave, and power frequency is 50Hz, and dutycycle is 1/100, and current density is 0.01A/dm 2, electroplating time is 1 minute.
When the large stretch of nickel plating aluminium flake for preparing was cut to nickel-plated aluminum lug, the area of large stretch of nickel plating aluminium flake was 1000 times of nickel-plated aluminum lug, and the width of nickel-plated aluminum lug is 200 millimeters.

Claims (2)

1. the method for a preparing nickel-plated aluminum tab by two-step electroplating is characterized in that the large stretch of nickel plating aluminium flake of preparation earlier, more large stretch of nickel plating aluminium flake is cut to nickel-plated aluminum lug, prepares large stretch of nickel plating aluminium flake and is made up of following two step plating step:
The solution formula of the first step nickel plating is in 1000ml solution: NiSO 46H 2O 240g～300g, NiCl 26H 2O 2g～20g, H 3BO 335g～55g, MgSO 47H 2O 30g～50g, tensio-active agent 0.01g～13.5g, 50 ℃～70 ℃ of bath temperatures, plating bath pH 3.1～5.5;
Described tensio-active agent is a concentration at one of sodium lauryl sulphate, X 2073 or TX10 of 0.1g/L～13.5g/L scope, or concentration is at one of Triple Pressed Stearic Acid, trimethyl-glycine, glycerin fatty acid ester or polysorbate of 0.01g/L～2.0g/L scope;
The solution formula of the second step nickel plating is in 1000ml solution: NiSO 46H 2O 200g～400g, NiCl 26H 2O 20g～100g, H 3BO 320g～50g, sodium lauryl sulphate 0.01g～13.5g, elementary brightening agent 0.1g～5g, second-class brightener 0.05g～2g, 45 ℃～75 ℃ of bath temperatures, pH3.2～5.2;
Two steps, galvanized current waveform was one of asymmetrical square wave, asymmetric sine wave, asymmetric CW, asymmetric choppy sea or pulse wave, or a kind of current waveform that is combined into of above-mentioned two kinds of waveforms; Power frequency is 0.1Hz～10000Hz, and dutycycle is 1/100～10000/100, and current density is 0.01A/dm 2～2.5A/dm 2, electroplating time is 0.1 second～35 minutes;
Described elementary brightening agent is one of asccharin, benzene sulfinic acid sodium salt, para toluene sulfonamide or unsaturated fatty acid derivative; Described second-class brightener is one of butynediol, propiolic alcohol or tonka bean camphor, or the reaction product of butynediol and oxyethane, or the reaction product of butynediol and epoxy chloropropane.
2. the method for a kind of preparing nickel-plated aluminum tab by two-step electroplating according to claim 1; When it is characterized in that described large stretch of nickel plating aluminium flake that will prepare is cut to nickel-plated aluminum lug; The area of large stretch of nickel plating aluminium flake is 3 times to 10000 times of nickel-plated aluminum lug, and the width of nickel-plated aluminum lug is any width between 1 millimeter to 200 millimeters; Here specify the size of nickel-plated aluminum lug to satisfy following relation: length＞width＞thickness.
CN2010102417158A 2010-07-30 2010-07-30 Method for preparing nickel-plated aluminum tab by two-step electroplating Expired - Fee Related CN101899695B (en)

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CN103160868A (en) * 2011-12-17 2013-06-19 鞍钢重型机械有限责任公司 Electrolyte for producing active nickel with sulfur and use method thereof
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CN100467675C (en) * 2005-11-25 2009-03-11 湖南大学 Process for directly electroplating on surface of aluminium or aluminium alloy
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