CN101864584B - Barrel plating electroplate liquid and battery steel shell method of barrel electroplating - Google Patents

Barrel plating electroplate liquid and battery steel shell method of barrel electroplating Download PDF

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Publication number
CN101864584B
CN101864584B CN201010185248.1A CN201010185248A CN101864584B CN 101864584 B CN101864584 B CN 101864584B CN 201010185248 A CN201010185248 A CN 201010185248A CN 101864584 B CN101864584 B CN 101864584B
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China
Prior art keywords
plating
barrel plating
electroplate liquid
barrel
acid
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CN201010185248.1A
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Chinese (zh)
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CN101864584A (en
Inventor
柳依玲
顾耀前
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上海金杨金属表面处理有限公司
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Publication of CN101864584A publication Critical patent/CN101864584A/en
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Abstract

The present invention relates to, for directly changing the process technique that chemical energy is used carrier on the device of electric energy, be specially a kind of barrel plating electroplate liquid and battery steel shell method of barrel electroplating.A kind of barrel plating electroplate liquid, is dissolved in water is formed by 80~120 or 200~350 portions of main salt, 30~100 parts of anode activation agent, 3~60 parts of buffer agents, 20~30 or 180~250 parts of chelating agent, 0.5~2.5 part of stress relieving agent, 0.005~0.1 part of main brightener and 0.3~1.0 part of adjuvant.A kind of battery steel shell method of barrel electroplating, is carried out by defat, barrel plating and three steps of bleaching successively to battery steel shell, during barrel plating, the pH value of electroplate liquid between 4.0~4.6 or 6.5~8.5, temperature 40~70 DEG C, electric current density 0.2~3A/dm2, drum rotating speed 4~12 revs/min, barrel plating time 180~300 minutes.Deposit appearance of the present invention is the brightest, and brightness is high, and corrosion strength is strong.

Description

Barrel plating electroplate liquid and battery steel shell method of barrel electroplating
Technical field
The present invention relates to, for directly changing the process technique that chemical energy is used carrier on the device of electric energy, be specially rolling Plating electroplate liquid and battery steel shell method of barrel electroplating.
Background technology
At present, alkaline battery is few with its capacitance height, length in service life, environmental pollution and obtains the most widely should With.The shell of alkaline battery is typically stamped to form with steel, and as container and the exit of electrode of electrolyte, battery case is wanted Asking that corrosion resistance is strong, good airproof performance, excellent conductivity, therefore battery steel shell is generally made Nickel Plating Treatment and is referred to improve properties Mark.Battery steel shell is typical blind-hole parts, and a lot of model is again deep-hole parts simultaneously, but the requirement to electrodeposited coating, As the highest with the conjugation of base material, the thickness of coating and bright degree in coating, therefore the plating difficulty of battery steel shell is the biggest.Tradition Sulfate nickel plating technology fastness, thickness and brightness all cannot meet the requirements on the inwall of blind hole deep hole and inner bottom surface deposit Nickel dam, therefore, all the time, the technique manufacturing commonly used first nickel plating punching press again of battery steel shell, and must also divide after punching press Shi Shi defat and antirust treatment.Use this processing method, owing to the steel hardness in nickel plating rear surface and stress all can increase And plasticity relative reduction, tonnage demand to equipment when which improves stamping-out drawing, weaken punch process.For making plating Remaining to after nickel keep original punch process, steel can only select the kind that quality is softer, and this results in rammed box hat Impact strength declines, and is susceptible to machinery and damages.Additionally, due to the lattice at nickel coating after punching press is destroyed, hole Gap rate increases, and punching press incision is without nickel coating, and the most this kind of box hat gets rusty easily, and the most therefore the battery storing cycle shortens. Finding by prior art documents, Chinese patent CN1484714A discloses one " for alkali on March 24th, 2004 The nickel-clad steel plate of property manganese cell positive pole tank and alkaline manganese battery positive pole tank ", anode tank (i.e. battery used for this technical scheme Shell) steel plate, intert one section of heat treatment step of operation in non-oxidizing atmosphere man-hour by adding, and carefully select electricity Plating bath during plating, electric current density, thus form nickel system diffusion coating on a surface of steel plate, this one side is as the interior table of tank Face;Ferrum-nickel diffusion coating and the nickel coating through recrystallization softening it is formed with, outside this one side is as tank on another surface Surface.Although this nickel-clad steel plate makes moderate progress in terms of the lattice and porosity of nickel coating, but the addition of heat treatment step and The requirement more harsh to plating bath, electric current density so that difficulty of processing is big, efficiency is low, cost is high, and punching press incision is without nickel The problem of coating is the most effectively solved.
Summary of the invention
For overcoming aforementioned the deficiencies in the prior art, the corrosion resistance solving the current battery steel shell obtained by nickel plating method is poor, The defect that intensity is low, the invention discloses a kind of barrel plating electroplate liquid and battery steel shell method of barrel electroplating.
A kind of barrel plating electroplate liquid, by main salt, anode activation agent, buffer agent, chelating agent, stress relieving agent, main brightener With adjuvant form, the mass fraction of each component is as described below: main salt 80~120 or 200~350, anode activation agent 30~ 100, buffer agent 3~60, chelating agent 20~30 or 180~250, stress relieving agent 0.5~2.5, main brightener 0.005~0.1, Adjuvant 0.3~1.0.Wherein: NiSO selected by main salt4;NiCl is selected in anode activation agent2;H selected by buffer agent3BO3、NH3·H2O With any one in ammonium citrate;It is any one that chelating agent is selected in 1-hydroxy ethylidene-1,1-diphosphonic acid, potassium pyrophosphate and sodium citrate Kind;Naphthalenedisulfonic acid, benzoic sulfimide, any in benzsulfamide and ortho-sulphobenzimide are selected in stress relieving agent A kind of;Main brightener selects Isosorbide-5-Nitrae-butynediols, alkynol propoxylated compounds, diethylin propine, propilolic alcohol, propilolic alcohol the third oxygen Any one in based compound and ethoxylated acetylenic alcohols compound;Adjuvant selects propine drone alkali metal salt, butyl ether drone alkali Any in the alkali metal salt of slaine, the alkali metal salt of allyl sulphonic acid, the alkali metal salt of propine sulfonic acid and vinyl sulfonic acid Two or more compounding with arbitrary proportion.Above each component is all dissolved in deionized water or tap water, is made into gross mass Number is the solution of 1000, obtains barrel plating electroplate liquid.
A kind of battery steel shell method of barrel electroplating, to the battery steel shell being stamped to form by ungrease treatment before A. plating, B. barrel plating and C. plating after bleaching three steps of process to carry out successively, C step plating after bleaching processes and carries out the most successively: three roads recovery → Cleaning → bleaching → cleaning → neutralization → pure water washes → and antirust → dehydration → be dried, citric acid, oxalic acid, hydroxyl second are selected in bleaching Any one in acid, 1-hydroxy ethylidene-1,1-diphosphonic acid and sulphuric acid, neutralizes select in sodium hydroxide, potassium hydroxide and sodium carbonate any One, the feature in step is: it is barrel plating electroplate liquid as claimed in claim 1 that B walks electroplate liquid used during barrel plating;Rolling During plating, the pH value of electroplate liquid controls 4.0~4.6 or 6.5~8.5, temperature 40 DEG C~70 DEG C, electric current density 0.05A/dm2~ 3A/dm2, drum rotating speed 4~12 revs/min, barrel plating time 180~300 minutes.
Described battery steel shell method of barrel electroplating, the feature in step is: before A step plating, ungrease treatment is the most successively Carry out:
I. deoil defat: with the battery steel shell that degreasing fluid washing is to be electroplated, wash temperature 50 ± 10 DEG C, wash time 20~ 40 minutes, it is 40 DEG C~the deionized water of 60 DEG C by temperature after completing or tap water cleans up, twice the most repeatedly, degreasing fluid It is made up of sodium hydroxide, sodium silicate, sodium carbonate, sulfonic acid analog anion surfactants and deionized water, the quality hundred of each component Proportion by subtraction concentration is as described below: sodium hydroxide 5%~10%, sodium silicate 2%~8%, sodium carbonate 1%~10%, sulphonic acids cloudy from Sub-surface activating agent 2%~5%, deionized water or tap water surplus, sulfonic acid analog anion surfactants selects dodecyl Sodium sulfonate or dodecylbenzene sodium sulfonate.
Ii acid-wash activation: deoil completing the i-th step the battery steel shell acid solution at room temperature pickling 1 of defat~3 minutes, complete Cheng Houyong deionized water or tap water clean up, twice the most repeatedly, pickle select mass percent concentration be 10%~ The hydrochloric acid of 45%, or the sulphuric acid that mass percent concentration is 10%~25%.
Use technical scheme disclosed in this invention, can fundamentally solve the technique institute of prior art nickel plating punching press again The drawback brought, various process parameters during owing to have employed special electroplate liquid and meticulously have selected barrel plating so that battery Box hat this kind of blind hole deep-hole type parts surface especially inner surface also can deposit and base material adhesion is strong, has certain thickness and light The nickel coating that bright degree is high, outer surface nickel coating thickness between 1.5 μm~6 μm, inwall nickel coating 0.1 μm~1.0 μm it Between, machining no longer implemented after nickel plating completes by such box hat, and nickel coating lattice is not damaged the densification remaining to keep original State, porosity is little, thus improves corrosion resistance, and during barrel plating, surfaces externally and internally and the incision of box hat can be plated Immersion does not has, and whole surface nickel coating does not has blind spot, so will not get rusty, the resting period of such battery is the most just greatly prolonged.Root According to contrast experiment, use the battery steel shell of technical scheme barrel plating disclosed in this invention, either in the environment of hot and humid, Still it is immersed in electrolyte solution, or in the metal salt solution that activity is lower than ferrum, the most both generated without rusty stain, also without gold Belong to replaced, the box hat that the nickel coating of densification is protected effectively is described, be allowed to completely cut off with corrosive atmosphere.And nickel coating outward appearance Bai Liang, be different from by nickel plated steel strip punching press make the ash that presented of battery steel shell dark-coloured, battery outward appearance is more attractive.
Accompanying drawing explanation
Fig. 1 is the image using its coating of battery steel shell of barrel plating of the present invention to be amplified to 400 times;
Fig. 2 is the image that its coating of battery steel using traditional first nickel plating Sheet Metal Forming Technology again to prepare is amplified to 400 times.
Detailed description of the invention
This utility model is further illustrated below by way of specific embodiment.
Embodiment 1
A. defat before plating:
I. deoil defat:
Take the box hat do not electroplated used by No. LR6 alkaline zinc-manganese battery to be placed in degreasing bath, pour degreasing fluid into and wash Washing, degreasing fluid is to be as the criterion whole for box hat submergences, and the mass percent concentration of each component of degreasing fluid is as described below: sodium hydroxide 5%, sodium silicate 2%, sodium carbonate 1%, dodecyl sodium sulfate 2%, tap water surplus.
During washing, the temperature in degreasing bath is 40 DEG C, wash time 20 minutes, is 40 DEG C go by temperature after having washed Ionized water or tap water clean up.Above-mentioned washing-cleaning process is repeated twice.
Ii acid-wash activation:
Deoiling completing the i-th step the battery steel shell acid solution at room temperature pickling 1 minute of defat, acid solution selects percent mass Specific concentration is the hydrochloric acid of 10%, and pickling cleans up with deionized water or tap water after completing.Above-mentioned pickling-cleaning process is repeatedly Carry out twice.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 4.00, temperature 50 C, electric current density 0.2A/dm2, drum rotating speed 4 revs/min, during barrel plating Between 180 minutes.
C. after bleaching is plated
Carrying out the most successively: three road recovery → cleaning → bleaching → cleaning → neutralization → pure water wash → and pure water washes → Antirust → dehydration → be dried.
Wherein, organic acid is selected during bleaching, such as citric acid, oxalic acid, hydroxyacetic acid or 1-hydroxy ethylidene-1,1-diphosphonic acid, it is possible to select Sulphuric acid.Sodium hydroxide, potassium hydroxide or sodium carbonate is selected during neutralization.Xu Guang company of upper village of Japan antirust agent is selected time antirust.
Embodiment 2
A. defat before plating:
I. deoil defat:
The mass percent concentration of each component of degreasing fluid is as described below: sodium hydroxide 7%, sodium silicate 5%, sodium carbonate 5%, Dodecylbenzene sodium sulfonate 3%, tap water surplus.
Temperature in degreasing bath is 50 DEG C, wash time 30 minutes, with the deionized water that temperature is 50 DEG C after having washed Or tap water cleans up.
Ii acid-wash activation:
Pickling 2 minutes, acid solution selects mass percent concentration to be the hydrochloric acid of 25%.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 4.30, temperature 53 DEG C, electric current density 0.4A/dm2, drum rotating speed 8 revs/min, during barrel plating Between 240 minutes.
Other steps are all with embodiment one.
Embodiment 3
A. defat before plating:
I. deoil defat:
The mass percent concentration of each component of degreasing fluid is as described below: sodium hydroxide 10%, sodium silicate 8%, sodium carbonate 10%, dodecyl sodium sulfate 5%, tap water surplus.
Temperature in degreasing bath is 60 DEG C, wash time 40 minutes, clear with the tap water that temperature is 60 DEG C after having washed Wash clean.
Ii acid-wash activation:
Pickling 3 minutes, acid solution selects mass percent concentration to be the hydrochloric acid of 45%.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 4.45, temperature 57 DEG C, electric current density 0.8A/dm2, drum rotating speed 12 revs/min, barrel plating 300 minutes time.
Other steps are all with embodiment one.
Embodiment 4
A. defat before plating:
I. deoil defat:
The mass percent concentration of each component of degreasing fluid is as described below: sodium hydroxide 5%, sodium silicate 2%, sodium carbonate 1%, Dodecylbenzene sodium sulfonate 2%, deionized water surplus.
Temperature in degreasing bath is 40 DEG C, wash time 20 minutes, clear with the tap water that temperature is 40 DEG C after having washed Wash clean.
Ii acid-wash activation:
Pickling 1 minute, acid solution selects mass percent concentration to be the sulphuric acid of 10%.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Component Select material Quality (g)
Main salt NiSO4 80
Anode activation agent NiCl2 50
Buffer agent Ammonium citrate 10
Chelating agent Potassium pyrophosphate 200
Stress relieving agent Naphthalenedisulfonic acid 2
Main brightener Isosorbide-5-Nitrae-butynediols 0.1
Adjuvant Propine drone sodium salt 0.8
The sodium salt of vinyl sulfonic acid 0.2
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 4.60, temperature 60 C, electric current density 1.0A/dm2
Other steps are all with embodiment one.
Embodiment 5
A. defat before plating:
I. deoil defat:
The mass percent concentration of each component of degreasing fluid is as described below: sodium hydroxide 8%, sodium silicate 5%, sodium carbonate 6%, Dodecyl sodium sulfate 4%, deionized water surplus.
Temperature in degreasing bath is 50 DEG C, wash time 30 minutes, with the deionized water that temperature is 50 DEG C after having washed Clean up.
Ii. acid-wash activation:
Pickling 2 minutes, acid solution selects mass percent concentration to be the sulphuric acid of 15%.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 6.50, temperature 50 C, electric current density 0.2A/dm2
Other steps are all with embodiment one.
Embodiment 6
A. defat before plating:
I. deoil defat:
The mass percent concentration of each component of degreasing fluid is as described below: sodium hydroxide 10%, sodium silicate 8%, sodium carbonate 10%, dodecylbenzene sodium sulfonate 5%, tap water surplus.
Temperature in degreasing bath is 60 DEG C, wash time 40 minutes, clear with the tap water that temperature is 60 DEG C after having washed Wash clean.
Ii acid-wash activation:
Pickling 3 minutes, acid solution selects mass percent concentration to be the sulphuric acid of 25%.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 6.70, temperature 53 DEG C, electric current density 0.4A/dm2
Other steps are all with embodiment one.
Embodiment 7
A. defat before plating:
I. deoil defat:
The mass percent concentration of each component of degreasing fluid is as described below: sodium hydroxide 5%, sodium silicate 2%, sodium carbonate 1%, Dodecyl sodium sulfate 2%, tap water surplus.
Temperature in degreasing bath is 40 DEG C, wash time 20 minutes, with the deionized water that temperature is 40 DEG C after having washed Or deionized water cleans up.
Ii. acid-wash activation:
Pickling 1 minute, acid solution selects mass percent concentration to be the hydrochloric acid of 10%.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 6.85, temperature 55 DEG C, electric current density 0.6A/dm2
Other steps are all with embodiment one.
Embodiment 8
A. defat before plating:
I. deoil defat:
The mass percent concentration of each component of degreasing fluid is as described below: sodium hydroxide 7%, sodium silicate 5%, sodium carbonate 5%, Dodecylbenzene sodium sulfonate 3%, tap water surplus.
Temperature in degreasing bath is 50 DEG C, wash time 30 minutes, clear with the tap water that temperature is 50 DEG C after having washed Wash clean.
Ii. acid-wash activation:
Pickling 2 minutes, acid solution selects mass percent concentration to be the hydrochloric acid of 25%.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.00, temperature 57 DEG C, electric current density 0.8A/dm2
Other steps are all with embodiment one.
Embodiment 9
A. defat before plating:
I. deoil defat:
The mass percent concentration of each component of degreasing fluid is as described below: sodium hydroxide 10%, sodium silicate 8%, sodium carbonate 10%, dodecyl sodium sulfate 5%, deionized water surplus.
Temperature in degreasing bath is 60 DEG C, wash time 40 minutes, with the deionized water that temperature is 60 DEG C after having washed Clean up.
Ii acid-wash activation:
Pickling 3 minutes, acid solution selects mass percent concentration to be the hydrochloric acid of 45%.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.15, temperature 60 C, electric current density 1A/dm2
Other steps are all with embodiment one.
Embodiment 10
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.30, temperature 50 C, electric current density 0.2A/dm2
Other steps are all with embodiment two.
Embodiment 11
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.45, temperature 53 DEG C, electric current density 0.5A/dm2
Other steps are all with embodiment two.
Embodiment 12
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.60, temperature 57 DEG C, electric current density 0.8A/dm2
Other steps are all with embodiment two.
Embodiment 13
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.75, temperature 60 C, electric current density 1A/dm2
Other steps are all with embodiment two.
Embodiment 14
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.90, temperature 65 DEG C, electric current density 0.5A/dm2
Other steps are all with embodiment two.
Embodiment 15
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 8.05, temperature 67 DEG C, electric current density 2A/dm2
Other steps are all with embodiment two.
Embodiment 16
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 8.20, temperature 70 C, electric current density 3A/dm2
Other steps are all with embodiment two.
Embodiment 17
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 6.5, temperature 65 DEG C, electric current density 0.5A/dm2
Other steps are all with embodiment two.
Embodiment 18
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 6.7, temperature 68 DEG C, electric current density 1.5A/dm2
Other steps are all with embodiment two.
Embodiment 19
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 6.85, temperature 70 C, electric current density 3A/dm2
Other steps are all with embodiment two.
Embodiment 20
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.00, temperature 65 DEG C, electric current density 0.5A/dm2
Other steps are all with embodiment two.
Embodiment 21
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.15, temperature 67 DEG C, electric current density 2A/dm2
Other steps are all with embodiment two.
Embodiment 22
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.30, temperature 70 C, electric current density 3A/dm2
Other steps are all with embodiment two.
Embodiment 23
A. defat before plating:
I. deoil defat:
Degreasing fluid is prepared by requirement as follows:
Component Mass percent concentration (%)
Commercially available degreasing agent 40
NaOH 10
Deionized water Surplus
The degreasing agent that Shanghai detergents and cosmetic company limited produces selected by commercially available degreasing agent.
Temperature in degreasing bath is 60 DEG C, wash time 40 minutes, with the deionized water that temperature is 60 DEG C after having washed Clean up.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.45, temperature 50 C, electric current density 0.05A/dm2
Other steps are all with embodiment one.
Embodiment 24
A. defat before plating:
I. deoil defat:
Degreasing fluid is prepared by requirement as follows:
Component Mass percent concentration (%)
Commercially available degreasing agent 45
NaOH 15
Tap water Surplus
The degreasing agent that Shanghai detergents and cosmetic company limited produces selected by commercially available degreasing agent.
Temperature in degreasing bath is 60 DEG C, wash time 40 minutes, clear with the tap water that temperature is 60 DEG C after having washed Wash clean.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.60, temperature 50 C, electric current density 0.08A/dm2
Other steps are all with embodiment one.
Embodiment 25
A. defat before plating:
I. deoil defat:
Degreasing fluid is prepared by requirement as follows:
Component Mass percent concentration (%)
Commercially available degreasing agent 50
NaOH 20
Tap water Surplus
The degreasing agent that Shanghai detergents and cosmetic company limited produces selected by commercially available degreasing agent
Temperature in degreasing bath is 60 DEG C, wash time 40 minutes, clear with the tap water that temperature is 60 DEG C after having washed Wash clean.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.75, temperature 55 DEG C, electric current density 0.08A/dm2
Other steps are all with embodiment one.
Embodiment 26
A. defat before plating:
I. deoil defat:
Degreasing fluid is prepared by requirement as follows:
Component Mass percent concentration (%)
Commercially available degreasing agent 60
NaOH 25
Tap water Surplus
The degreasing agent that Shanghai detergents and cosmetic company limited produces selected by commercially available degreasing agent.
Temperature in degreasing bath is 60 DEG C, wash time 40 minutes, clear with the tap water that temperature is 60 DEG C after having washed Wash clean.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 7.90, temperature 55 DEG C, electric current density 0.1A/dm2
Other steps are all with embodiment one.
Embodiment 27
A. defat before plating:
I. deoil defat:
Degreasing fluid is prepared by requirement as follows:
Component Mass percent concentration (%)
Commercially available degreasing agent 40
NaOH 10
Tap water Surplus
The degreasing agent that Shanghai detergents and cosmetic company limited produces selected by commercially available degreasing agent.
Temperature in degreasing bath is 60 DEG C, wash time 40 minutes, clear with the tap water that temperature is 60 DEG C after having washed Wash clean.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 8.05, temperature 50 C, electric current density 0.05A/dm2
Other steps are all with embodiment one.
Embodiment 28
A. defat before plating:
I. deoil defat:
Degreasing fluid is prepared by requirement as follows:
Component Mass percent concentration (%)
Commercially available degreasing agent 50
NaOH 15
Tap water Surplus
The degreasing agent that Shanghai detergents and cosmetic company limited produces selected by commercially available degreasing agent.
Temperature in degreasing bath is 60 DEG C, wash time 40 minutes, clear with the tap water that temperature is 60 DEG C after having washed Wash clean.
Ii. acid-wash activation:
Pickling 3 minutes, acid solution selects mass percent concentration to be the sulphuric acid of 25%.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Component Select material Quality (g)
Main salt NiSO4 300
Anode activation agent NiCl2 40
Buffer agent H3BO3 45
Chelating agent Sodium citrate 20
Stress relieving agent Naphthalenedisulfonic acid 0.5
Main brightener Alkynol propoxylated compounds 0.05
Adjuvant Butyl ether drone sodium salt 0.2
The sodium salt of propine sulfonic acid 0.3
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 8.20, temperature 50 C, electric current density 0.08A/dm2
Other steps are all with embodiment one.
Embodiment 29
A. defat before plating:
I. deoil defat:
Degreasing fluid is prepared by requirement as follows:
Component Mass percent concentration (%)
Commercially available degreasing agent 55
NaOH 20
Tap water Surplus
The degreasing agent that Shanghai detergents and cosmetic company limited produces selected by commercially available degreasing agent.
Temperature in degreasing bath is 60 DEG C, wash time 40 minutes, clear with the tap water that temperature is 60 DEG C after having washed Wash clean.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 8.35, temperature 55 DEG C, electric current density 0.08A/dm2
Other steps are all with embodiment one.
Embodiment 30
A. defat before plating:
I. deoil defat:
Degreasing fluid is prepared by requirement as follows:
Component Mass percent concentration (%)
Commercially available degreasing agent 60
NaOH 25
Tap water Surplus
The degreasing agent that Shanghai detergents and cosmetic company limited produces selected by commercially available degreasing agent.During preparation degreasing fluid, it is also possible to use Tap water replaces deionized water.
Temperature in degreasing bath is 60 DEG C, wash time 40 minutes, clear with the tap water that temperature is 60 DEG C after having washed Wash clean.
B. barrel plating:
The box hat completing the aforementioned A front ungrease treatment of step plating is put in barrel plating tank, pours electroplate liquid into and carry out barrel plating, plating Liquid is prepared by requirement as follows:
Above each component is all dissolved in deionized water, is made into the solution that gross mass is 1000g, obtains barrel plating electroplate liquid. During barrel plating, the pH value of electroplate liquid controls 8.50, temperature 55 DEG C, electric current density 0.1A/dm2
Other steps are all with embodiment one.
Contrast experiment 1
The battery steel shell prepared with method described in embodiment 2, is set to sample A;Another with traditional first nickel plating Sheet Metal Forming Technology again The battery steel shell prepared, is set to sample B.
Sample A and sample B respectively takes 5, measures the thickness of coating of outer wall, and data are as shown in the table:
Sample Position 1 2 3 4 5 Meansigma methods
A Outer wall 2.50 2.76 2.37 2.68 2.67 2.596
B Outer wall 1.96 2.01 2.09 2.00 1.99 2.01
As seen from the above table, the outer wall coating of sample A is than thick about the 30% of sample B.
Fig. 1 is the image that the coating of sample A is amplified to 400 times, and Fig. 2 is the image that the coating of sample B is amplified to 400 times, It is apparent that the densification that the coating of sample A is than sample B is much.
Contrast experiment 2
High temperature and humidity test contrasts: by sample A and sample B simultaneously 65 DEG C, the environment of 90% humidity is placed five hours Rear taking-up, sample A outer wall or inwall are all without rusty stain, and sample B outer wall and inwall have rusty stain to generate.Illustrate with this The battery case that bright disclosed method prepares, plated layer compact adhesive force is strong, can effectively steel and extraneous corrosivity atmosphere every Absolutely, thus play the effect of protection.
Contrast experiment 3
Bluepoint Experimental Comparison: by the filter paper potassium ferricyanide+sodium chloride solution moistening, after be covered each by sample A and sample B Upper 5 minute.The not aobvious blueness of the filter paper of sample A, the aobvious blueness of the filter paper of sample B.Explanation the method disclosed in the present prepares Battery steel shell, coating is uniformly without blind spot, and otch also has the coating of densification to cover, and improves corrosion strength and the life-span of shell.
Contrast experiment 4
Copper sulfate soak test contrasts: by sample A and sample B, all in the CuSO4 solution of 5%, submergence was taken out after 2 minutes, The outer wall of sample A and inwall are still in the silvery white of original light, and the outer wall of sample B and inwall have a small amount of copper to separate out.Ferrum with The reaction equation of copper sulfate is as follows:
Fe+CuSO4=FeSO4+Cu
There is not chemical reaction in Ni Yu CuSO4.
The battery case that explanation prepares by the method disclosed in the present, plated layer compact adhesive force is strong, can effectively steel with Extraneous corrosivity atmosphere isolation, thus play the effect of protection.
Contrast experiment 5
Salt water immersion test contrasts: by sample A and sample B, all in the NaCl solution of 5%, submergence was taken out after 2 hours, sample Product A otch, outer wall or inwall are all without rusty stain, and sample B otch, outer wall and inwall have rusty stain to generate.Illustrate with this The battery case that method disclosed in invention prepares, coating is uniformly without blind spot, and otch also has the coating of densification to cover, and improves shell Corrosion strength and life-span.Plated layer compact adhesive force is strong, effectively steel and the isolation of extraneous corrosivity atmosphere, thus can play protection Effect.
Contrast experiment 6
Salt spray test contrasts: take out after all using the NaCl solution of 5% to spray continuously 1 hour sample A and sample B, sample A Outer wall or inwall are all without rusty stain, and sample B outer wall and inwall have rusty stain to generate.Illustrate to use side disclosed in this invention The battery case that method prepares, plated layer compact adhesive force is strong, effectively steel and the isolation of extraneous corrosivity atmosphere, thus can play guarantor The effect protected.

Claims (2)

1. a barrel plating electroplate liquid, by main salt, anode activation agent, buffer agent, chelating agent, stress relieving agent, main brightener and Adjuvant forms, and it is characterized in that: the mass fraction of each component is as described below:
Main salt 80~120 or 200~350, anode activation agent 30~100, buffer agent 3~60, chelating agent 20~30 or 180~ 250, stress relieving agent 0.5~2.5, main brightener 0.005~0.1, adjuvant 0.3~1.0,
Wherein:
NiSO selected by main salt4
NiCl is selected in anode activation agent2
H selected by buffer agent3BO3、NH3·H2Any one in O and ammonium citrate;
Any one in 1-hydroxy ethylidene-1,1-diphosphonic acid, potassium pyrophosphate and sodium citrate selected by chelating agent;
Naphthalenedisulfonic acid or ortho-sulphobenzimide are selected in stress relieving agent;
Main brightener selects any one in alkynol propoxylated compounds, diethylin propine and ethoxylated acetylenic alcohols compound;
Any two in the alkali metal salt of propine drone alkali metal salt, butyl ether drone alkali metal salt and propine sulfonic acid selected by adjuvant Plant or two or more compounding with arbitrary proportion;
Above each component is all dissolved in deionized water or tap water, is made into the solution that gross mass number is 1000, obtain barrel plating and use Electroplate liquid.
2. a battery steel shell method of barrel electroplating, to the battery steel shell being stamped to form by ungrease treatment before A. plating, B. barrel plating and C. Plating after bleaching three steps of process to carry out successively, C step plating after bleaching processes and carries out the most successively: three roads recovery → and clearly Wash → bleach → clean → neutralize → pure water washes → antirust → dehydration → be dried, bleaching select citric acid, oxalic acid, hydroxyacetic acid, Any one in 1-hydroxy ethylidene-1,1-diphosphonic acid and sulphuric acid, neutralizes select in sodium hydroxide, potassium hydroxide and sodium carbonate any one Kind, it is characterized in that:
Before A step plating, ungrease treatment is carried out the most successively:
I. deoil defat: with the battery steel shell that degreasing fluid washing is to be electroplated, wash temperature 50 ± 10 DEG C, wash time 20~40 points Clock, is 40 DEG C~the deionized water of 60 DEG C by temperature after completing or tap water cleans up, twice the most repeatedly, degreasing fluid is by hydrogen Sodium oxide, sodium silicate, sodium carbonate, sulfonic acid analog anion surfactants and deionized water composition, the mass percent of each component Concentration is as described below: sodium hydroxide 5%~10%, sodium silicate 2%~8%, sodium carbonate 1%~10%, sulfonic acid analog anion table Face activating agent 2%~5%, deionized water surplus, sulfonic acid analog anion surfactants selects dodecyl sodium sulfate or 12 Sodium alkyl benzene sulfonate;
Ii. acid-wash activation: deoil completing the i-th step the battery steel shell acid solution at room temperature pickling 1 of defat~3 minutes, complete Clean up with deionized water or tap water afterwards, twice the most repeatedly, pickle select mass percent concentration be 10%~ The hydrochloric acid of 45%, or the sulphuric acid that mass percent concentration is 10%~25%;
It is barrel plating electroplate liquid as claimed in claim 1 that B walks electroplate liquid used during barrel plating;During barrel plating, the pH of electroplate liquid Value controls 4.0~4.6 or 6.5~8.5, temperature 40 DEG C~70 DEG C, electric current density 0.05A/dm2~3A/dm2, drum rotating speed 4 ~12 revs/min, barrel plating time 180~300 minutes.
CN201010185248.1A 2010-05-26 2010-05-26 Barrel plating electroplate liquid and battery steel shell method of barrel electroplating CN101864584B (en)

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CN102021619B (en) * 2010-12-10 2012-07-11 广州晋惠化工科技有限公司 Electronickelling alloy solution for improving corrosion resistance of coating
CN102534695B (en) * 2010-12-29 2015-06-17 京东方科技集团股份有限公司 Metal substrate for flexible display and preparation method for metal substrate
CN105350033A (en) * 2015-11-24 2016-02-24 安徽天思朴超精密模具股份有限公司 Material combination of anticorrosion electroplating liquid and preparation method and application of anticorrosion electroplating liquid
CN105696031A (en) * 2015-12-01 2016-06-22 江苏九天光电科技有限公司 Method for manufacturing steel power lithium battery shell by using nickel pre-electroplated steel band
CN105506722A (en) * 2015-12-29 2016-04-20 上海金杨金属表面处理有限公司 Battery shell discharge disc barrel plating device
CN105951144A (en) * 2016-06-21 2016-09-21 贵州振华群英电器有限公司(国营第八九厂) Nickel plating process for deep-hole part
CN109137003A (en) * 2018-08-09 2019-01-04 福鼎恒晟金属表面科技有限公司 A kind of nickel plating technology of clipper
CN110484945A (en) * 2019-09-03 2019-11-22 福建南平南孚电池有限公司 Electroplate liquid and use its shell electric plating method to battery
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