CN113174613B - Preparation method of sulfur-free nickel button - Google Patents

Preparation method of sulfur-free nickel button Download PDF

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CN113174613B
CN113174613B CN202110386632.6A CN202110386632A CN113174613B CN 113174613 B CN113174613 B CN 113174613B CN 202110386632 A CN202110386632 A CN 202110386632A CN 113174613 B CN113174613 B CN 113174613B
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nickel
button
sulfur
electrolyte
base
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CN113174613A (en
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郭勇
李亦婧
卢晓锋
王旭生
王帅
王磊
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/06—Operating or servicing
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

The invention discloses a preparation method of a sulfur-free nickel button, and belongs to the field of hydrometallurgy. The invention grows the base button in the first-stage electrolyte with sulfur-containing additive, and then grows the finished nickel button in the second-stage electrolyte without sulfur. The internal stress of the electrolyte is reduced by the brightening agent and the leveling agent in one section of electrolyte, so that the internal stress of the grown base buckle is low, the nickel buckle is ensured not to tilt, and the surface is smooth and flat; the second-stage electrolyte does not contain sulfur-containing additives, so that sulfur is not contained in the nickel simple substance deposited by the cathode, the sulfur content in the nickel button is diluted, the nickel button is prevented from tilting and falling off in the growth process, the surface is smooth and flat, the nickel button is easy to separate from the polar plate, and the nickel button has good application prospect.

Description

Preparation method of sulfur-free nickel button
Technical Field
The invention relates to a preparation method of a sulfur-free nickel button, belonging to the field of hydrometallurgy.
Background
Nickel buttons are an anode material for nickel plating. The appearance of the titanium alloy is in a flat button shape, so that the titanium alloy has good fluidity, the filling density in the anode titanium basket is high, and the phenomenon of tower bridge is avoided; the anode area is stable and uniform, the phenomenon of anode 'cavitation' is avoided, the electroplating production is very beneficial, and meanwhile, the mechanical automation addition is convenient; the nickel button has the characteristics of large blunting current density and small blunting area in the electroplating process, so that the nickel button is widely applied to industries such as wire cutting, electronics, crystallizers, electroforming and the like. The nickel buckles are divided into sulfur-containing nickel buckles and sulfur-free nickel buckles, the sulfur content requirement of the sulfur-free nickel buckles is less than 0.0008%, and the sulfur-free nickel buckles are mainly applied to the field of corrosion-resistant electroplating. The nickel buckle with high tensile stress is easy to present a layered structure, the buckle edge is in a curling state, and the buckle edge is easy to fall off from the polar plate in the growing process. While most of the additives with stress adjustment function are sulfur-containing compounds, and the additives added into the electrolyte react with nickel together in the cathode to generate Ni x S y The sulfur content of the nickel button exceeds the standard.
Disclosure of Invention
In order to solve the problems that the nickel buckle is easy to present a layered structure and the buckle edge is in a curling state and easy to fall off from the polar plate in the growing process caused by high tensile stress in the production of the sulfur-free nickel buckle, the preparation method of the sulfur-free nickel buckle is provided to inhibit the tensile stress of electrolyte for leveling the nickel buckle on the polar plate and simultaneously ensure that the sulfur content of the nickel buckle meets the requirement.
The invention relates to a preparation method of a sulfur-free nickel button, which comprises the steps of firstly electrolytically growing a base button with a certain thickness in a first-stage electrolyte containing a sulfur-containing stress regulator with low current, and then growing the base button in a second-stage electrolyte containing no additive, so as to obtain the sulfur-free nickel button which has a flat and bright appearance, is easy to peel and has the sulfur content of less than 0.0008 percent. The method specifically comprises the following process steps:
(1) Heating and dissolving the leveling agent in deionized water, cooling to room temperature without solid precipitation, and respectively adding one class of brightening agent and two classes of brightening agent, stirring and dissolving to obtain the base buckle additive solution. Wherein the leveling agent is at least one of methacrylate and 2, 6-pyridine dicarboxylic acid; the brightening agent is at least one of saccharin sodium, sodium benzenesulfonate and sodium styrenesulfonate; the brightening agent is at least one of 1, 4-butynediol, ethoxylated propargyl alcohol and coumarin.
(2) Adding the base buckle additive solution into the base electrolyte to obtain a first-stage electrolyte; heating a section of electrolyte to 60-70 ℃, and placing a cathode plate special for a nickel buckle and a metal nickel anode into an electrolytic tank for electrolysis: the current density is controlled to be 110-240A/m 2 And (5) carrying out electrolysis for 4-24 hours, and taking out to obtain the long-base buckling pole plate.
In the basic nickel electrolyte, the concentration of each component is 80-120 g/L of nickel sulfate, 26-95 g/L of nickel chloride, 10-30 g/L of sodium sulfate, 10-30 g/L of sodium chloride and pH=4.5-5.0. In the electrolyte, the concentration of the leveling agent is 10-260 mg/L, the concentration of the first brightening agent is 30-400 mg/L, and the concentration of the second brightening agent is 5-75 mg/L.
(3) Placing the polar plate with the base buckle into a two-stage electrolyte (basic nickel electrolyte), and controlling the electrolytic current density to 240A/m 2 ~560A/m 2 The electrolysis time is 144-240 hours; after the nickel button electrolysis is completed, take outThe nickel button polar plate vibrates to separate the nickel button from the template, and the sulfur-free nickel button finished product is obtained.
The prepared base buckle (the nickel buckle obtained by one-stage electrolysis has the advantages that the nickel buckle obtained by one-stage electrolysis has short time and small buckle with low current, the nickel buckle obtained by one-stage electrolysis plays a role similar to a template, and is called as the base buckle), the weight of the base buckle is 0.17-0.57 g, and the weight of the finished nickel buckle is 18-30 g. The crystal of the sulfur-free nickel button is compact, the appearance is smooth, and the appearance is in a regular button shape. The mass percentage of the sulfur element in the nickel button is less than 0.0008 percent.
And detecting the internal stress of the nickel coating by adopting a strip cathode method. The result shows that the internal stress of the nickel coating obtained by electrolysis in the process of adding a section of electrolyte is-0.3-0.5 kg/mm 2 The internal stress of the nickel coating obtained by adding the two-stage electrolyte is-0.3-0.5 kg/mm 2 . The internal stress of the electrolytic nickel button in the two-stage electrolyte is insufficient to deform the base button. )
Compared with the prior art, the invention has the following advantages: the tensile stress of the nickel button produced by the electrolyte without the additive is overlarge, and the electrolysis is divided into two steps for producing the sulfur-free nickel button: the first step, growing a base buckle in a section of electrolyte, wherein the section of electrolyte contains a brightening agent and a leveling agent to reduce the internal stress of the electrolyte, so that the grown base buckle has low internal stress and a smooth and flat surface, and the base buckle obtained by the section of electrolysis plays a role similar to a template due to the fact that the section of electrolysis time is short and the current is low and the grown buckle is small; and secondly, continuously growing the finished product buckle in the secondary electrolyte, wherein the secondary electrolyte does not contain sulfur-containing additives, so that the elementary substance of the nickel deposited by the cathode does not contain sulfur, thereby diluting the sulfur content in the nickel buckle, and simultaneously, the base buckle has certain thickness and mechanical strength, and is used as a template to be placed in the secondary electrolyte with larger stress for continuous growth, and the internal stress of the secondary nickel buckle is insufficient to deform the base buckle, so that the finally obtained finished product nickel buckle has a smooth appearance.
Detailed Description
The preparation of the sulfur-free nickel button of the present invention is further illustrated by the following specific examples.
Example 1
(1) Preparing a basic nickel electrolyte in an electrolytic tank according to 90g/L of nickel sulfate, 40g/L of nickel chloride, 20g/L of sodium chloride and 20g/L of sodium sulfate, wherein the pH=4.5;
(2) Stirring and dissolving 2, 6-pyridine dicarboxylic acid in hot water at 60 ℃, cooling to room temperature without solid precipitation, respectively adding saccharin sodium, sodium benzene sulfinate, sodium styrene sulfonate and 1, 4-butynediol, and stirring and dissolving to obtain a sulfur-containing nickel buckle additive aqueous solution. The dosage of each component in the sulfur-containing nickel button additive aqueous solution is measured according to the concentration of saccharin sodium 90mg/L, sodium benzenesulfonate 85mg/L, sodium styrenesulfonate 85mg/L, 1, 4-butynediol 10mg/L and 2, 6-pyridine dicarboxylic acid 15mg/L in the primary electrolyte;
(3) Adding an additive aqueous solution into a basic nickel electrolyte to obtain a section of electrolyte, heating the solution to 60 ℃, and placing a cathode plate special for a nickel buckle and a metal nickel anode into an electrolytic tank for electrolysis under the following electrolysis conditions: the current density of the first stage is controlled to be 110A/m 2 Taking out after 8 hours of electrolysis to obtain a pole plate with a base button;
(4) Placing the plate with base buckle into two-stage electrolyte (base electrolyte), and controlling electrolytic current density at 240A/m 2 The electrolysis time was 240 hours. And after the nickel button electrolysis is completed, taking out the nickel button polar plate and vibrating to separate the nickel button from the template. The weight of the base button is 0.17g, the weight of the finished nickel button is 11.3g, the crystal is compact, the appearance is smooth, and the appearance is regular button-shaped. The sulfur content of the nickel button is 0.0005%.
Example 2
(1) Preparing a basic nickel electrolyte in an electrolytic tank according to 90g/L of nickel sulfate, 50g/L of nickel chloride, 30g/L of sodium chloride and 10g/L of sodium sulfate, wherein the pH=4.9;
(2) Stirring and dissolving 2, 6-pyridine dicarboxylic acid in hot water at 80 ℃, cooling to room temperature without solid precipitation, respectively adding saccharin sodium and sodium benzenesulfonate, and stirring and dissolving coumarin to obtain sulfur-containing nickel buckle additive aqueous solution. The dosage of each component in the sulfur-containing nickel button additive aqueous solution is measured according to the concentration of saccharin sodium 90mg/L, sodium benzenesulfonate 90mg/L, sodium styrenesulfonate 30mg/L, coumarin 5mg/L and 2, 6-pyridine dicarboxylic acid 5mg/L in the primary electrolyte;
(3) Adding the additive aqueous solutionAdding the electrolyte into basic nickel electrolyte to obtain a section of electrolyte, heating the solution to 65 ℃, and then placing a cathode plate special for the nickel buckle and a metal nickel anode into an electrolytic tank for electrolysis under the following electrolysis conditions: the current density of the first stage is controlled to be 110A/m 2 After electrolysis for 12 hours, the mixture was taken out. Obtaining a pole plate with a base buckle;
(4) Placing the plate with the base buckle into a two-stage electrolyte (base nickel electrolyte), and controlling the electrolytic current density at 440A/m 2 Electrolysis was carried out for 144 hours. And after the nickel button electrolysis is completed, taking out the nickel button polar plate and vibrating to separate the nickel button from the template. The weight of the base button is 0.26g, the weight of the finished nickel button is 12.1g, the crystal is compact, the appearance is smooth, and the appearance is regular button-shaped. The sulfur content of the nickel button is 0.0006 percent.
Example 3
(1) Preparing a basic nickel electrolyte in an electrolytic tank according to 80g/L of nickel sulfate, 58g/L of nickel chloride, 10g/L of sodium chloride and 30g/L of sodium sulfate, wherein the pH=4.8;
(2) Stirring and dissolving 2, 6-pyridine dicarboxylic acid in hot water at 70 ℃, cooling to room temperature without solid precipitation, and respectively adding saccharin sodium, sodium benzenesulfonate, sodium styrenesulfonate, ethoxylated propargyl alcohol and methacrylate for stirring and dissolving to obtain a sulfur-containing nickel buckle additive aqueous solution. The dosage of each component in the sulfur-containing nickel button additive aqueous solution is calculated according to the concentration of 66mg/L saccharin sodium, 35mg/L sodium benzenesulfonate, 50mg/L sodium styrenesulfonate, 5mg/L ethoxylated propargyl alcohol, 70mg/L methacrylate and 10 mg/L2, 6-pyridine dicarboxylic acid in the primary electrolyte;
(3) Adding an additive aqueous solution into a basic nickel electrolyte to obtain a section of electrolyte, heating the solution to 65 ℃, and placing a cathode plate special for a nickel buckle and a metal nickel anode into an electrolytic tank for electrolysis under the following electrolysis conditions: the current density of the first stage is controlled to be 110A/m 2 Taking out after electrolysis for 24 hours to obtain a base button plate;
(4) Placing the plate with the base buckle into a two-stage electrolyte (base nickel electrolyte), and controlling the electrolytic current density at 440A/m 2 The electrolysis time was 168 hours. And after the nickel button electrolysis is completed, taking out the nickel button polar plate and vibrating to separate the nickel button from the template. The weight of the base button is 0.51g,the weight of the finished nickel button is 14.2g, the crystal is compact, the appearance is smooth, and the appearance is in a regular button shape. The sulfur content of the nickel button is 0.0008 percent.
Example 4
(1) Preparing a basic nickel electrolyte in an electrolytic tank according to 115g/L of nickel sulfate, 30g/L of nickel chloride, 30g/L of sodium chloride and 15g/L of sodium sulfate, wherein the pH=5.0;
(2) Stirring and dissolving 2, 6-pyridine dicarboxylic acid in hot water at 60 ℃, cooling to room temperature without solid precipitation, and respectively adding saccharin sodium, sodium benzenesulfonate, sodium styrenesulfonate, coumarin and methacrylate for stirring and dissolving to obtain sulfur-containing nickel buckle additive aqueous solution. In the sulfur-containing nickel button additive aqueous solution, the dosage of each component is calculated according to 80mg/L of saccharin sodium, 80mg/L of sodium benzenesulfonate, 50mg/L of sodium styrenesulfonate, 15mg/L of coumarin, 70mg/L of methacrylate and 10mg/L of 2, 6-pyridine dicarboxylic acid in the primary electrolyte;
(3) Adding an additive aqueous solution into a basic nickel electrolyte to obtain a section of electrolyte, heating the solution to 65 ℃, and placing a cathode plate special for a nickel buckle and a metal nickel anode into an electrolytic tank for electrolysis under the following electrolysis conditions: the current density of the first stage is controlled to be 180A/m 2 And (5) taking out after 8 hours of electrolysis to obtain the long base button plate.
(4) Placing the plate with the base buckle into a two-stage electrolyte (base nickel electrolyte), and controlling the electrolytic current density at 540A/m 2 The electrolysis time was 168 hours. And after the nickel button electrolysis is completed, taking out the nickel button polar plate and vibrating to separate the nickel button from the template. The weight of the base button is 0.28g, the weight of the finished nickel button is 17.2g, the crystal is compact, the appearance is smooth, and the appearance is regular button-shaped. The sulfur content of the nickel button is 0.0007 percent.
Example 5
(1) Preparing a basic nickel electrolyte in an electrolytic tank according to 110g/L of nickel sulfate, 95g/L of nickel chloride, 10g/L of sodium chloride and 15g/L of sodium sulfate, wherein the pH=5.0;
(2) Stirring and dissolving 2, 6-pyridine dicarboxylic acid in hot water at 65 ℃, cooling to room temperature without solid precipitation, respectively adding saccharin sodium and sodium benzenesulfonate 1, 4-butynediol, and stirring and dissolving to obtain sulfur-containing nickel buckle additive aqueous solution. The dosage of each component in the sulfur-containing nickel button additive aqueous solution is calculated according to the concentration of saccharin sodium in the primary electrolyte of 95mg/L, sodium benzenesulfonate of 95mg/L,1, 4-butynediol of 15mg/L, ethoxylated propargyl alcohol of 5mg/L and 2, 6-pyridine dicarboxylic acid of 15 mg/L;
(3) Adding an additive aqueous solution into a basic nickel electrolyte to obtain a section of electrolyte, heating the solution to 65 ℃, and placing a cathode plate special for a nickel buckle and a metal nickel anode into an electrolytic tank for electrolysis under the following electrolysis conditions: the current density of the first stage is controlled to be 240A/m 2 Taking out after 4 hours of electrolysis to obtain a base button plate;
(4) Placing the plate with the base buckle into a two-stage electrolyte (base nickel electrolyte), and controlling the electrolytic current density at 560A/m 2 The electrolysis time was 192 hours. And after the nickel button electrolysis is completed, taking out the nickel button polar plate and vibrating to separate the nickel button from the template. The weight of the base button is 0.19g, the weight of the finished nickel button is 20.2g, the crystal is compact, the appearance is smooth, and the appearance is regular button-shaped. The sulfur content of the nickel button is 0.0005%.
Example 6
(1) Preparing a basic nickel electrolyte in an electrolytic tank according to 110g/L of nickel sulfate, 95g/L of nickel chloride, 15g/L of sodium chloride and 10g/L of sodium sulfate, wherein the pH=5.0;
(2) Stirring and dissolving 2, 6-pyridine dicarboxylic acid in hot water at 65 ℃, cooling to room temperature without solid precipitation, and respectively adding saccharin sodium, sodium benzenesulfonate, sodium styrenesulfonate and 1, 4-butynediol for stirring and dissolving to obtain sulfur-containing nickel buckle additive aqueous solution. The dosage of each component in the sulfur-containing nickel button additive aqueous solution is calculated according to the concentration of saccharin sodium in the primary electrolyte of 74mg/L, sodium benzenesulfonate of 75mg/L, sodium styrenesulfonate of 35mg/L,1, 4-butynediol of 15mg/L and 2, 6-pyridine dicarboxylic acid of 15 mg/L;
(3) Adding an additive aqueous solution into a basic nickel electrolyte to obtain a section of electrolyte, heating the solution to 70 ℃, and placing a cathode plate special for a nickel buckle and a metal nickel anode into an electrolytic tank for electrolysis under the following electrolysis conditions: the current density of the first stage is controlled to be 240A/m 2 Taking out after electrolysis for 6 hours to obtain a base button plate;
(4) Will grow the base buckle polar platePlacing into two-stage electrolyte (basic nickel electrolyte), and controlling electrolytic current density at 440A/m 2 The electrolysis time was 192 hours. And after the nickel button electrolysis is completed, taking out the nickel button polar plate and vibrating to separate the nickel button from the template. The weight of the base button is 0.28g, the weight of the finished nickel button is 16g, the crystal is compact, the appearance is smooth, and the appearance is regular button-shaped. The sulfur content of the nickel button is 0.0006 percent.

Claims (6)

1. The preparation method of the sulfur-free nickel button comprises the following process steps:
(1) Heating and dissolving the leveling agent in deionized water, cooling to room temperature without solid precipitation, and respectively adding one type of brightening agent and two types of brightening agent, stirring and dissolving to obtain a base buckle additive solution;
(2) Adding the base buckle additive solution into the base electrolyte to obtain a first-stage electrolyte; heating a section of electrolyte to 60-70 ℃, and placing a cathode plate special for a nickel buckle and a metal nickel anode into an electrolytic tank for electrolysis: the current density is controlled to be 110-240A/m 2 Taking out after 4-24 hours of electrolysis to obtain a pole plate with a base;
(3) Placing the polar plate with the base button into a base nickel electrolyte, and controlling the current density to be 240A/m 2 ~560A/m 2 Electrolysis is carried out for 144-240 hours; and after the electrolysis of the nickel button is completed, taking out the nickel button polar plate and vibrating to separate the nickel button from the template, so as to obtain a sulfur-free nickel button finished product.
2. The method for preparing the sulfur-free nickel button according to claim 1, wherein the method comprises the following steps: the leveling agent is at least one of methacrylate and 2, 6-pyridine dicarboxylic acid.
3. The method for preparing the sulfur-free nickel button according to claim 1, wherein the method comprises the following steps: the brightening agent is at least one of saccharin sodium, sodium benzenesulfonate and sodium styrenesulfonate.
4. The method for preparing the sulfur-free nickel button according to claim 1, wherein the method comprises the following steps: the brightening agent is at least one of 1, 4-butynediol, ethoxylated propargyl alcohol and coumarin.
5. The method for preparing the sulfur-free nickel button according to claim 1, wherein the method comprises the following steps: in the basic nickel electrolyte, the concentration of each component is 80-120 g/L of nickel sulfate, 26-95 g/L of nickel chloride, 10-30 g/L of sodium sulfate, 10-30 g/L of sodium chloride and pH=4.5-5.0.
6. The method for preparing the sulfur-free nickel button according to claim 1, wherein the method comprises the following steps: in the electrolyte, the concentration of the leveling agent is 10-260 mg/L, the concentration of the first brightening agent is 30-400 mg/L, and the concentration of the second brightening agent is 5-75 mg/L.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019127645A (en) * 2018-01-26 2019-08-01 市原　祥次 Electrolytic nickel plating method including heat treatment process
CN110820034A (en) * 2018-08-08 2020-02-21 上海睿福有色金属有限公司 Nickel button production method
CN111945191A (en) * 2020-08-13 2020-11-17 中国科学院兰州化学物理研究所 Additive for sulfur-containing nickel button and preparation and application thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019127645A (en) * 2018-01-26 2019-08-01 市原　祥次 Electrolytic nickel plating method including heat treatment process
CN110820034A (en) * 2018-08-08 2020-02-21 上海睿福有色金属有限公司 Nickel button production method
CN111945191A (en) * 2020-08-13 2020-11-17 中国科学院兰州化学物理研究所 Additive for sulfur-containing nickel button and preparation and application thereof

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