CN109680310B

CN109680310B - Nickel-antimony electroplating solution and preparation method thereof

Info

Publication number: CN109680310B
Application number: CN201910007990.4A
Authority: CN
Inventors: 郑小美; 张朋越; 黄凌; 屠国平; 陶姗
Original assignee: China Jiliang University
Current assignee: JIANGSU OLITER ENERGY TECHNOLOGY CO LTD
Priority date: 2019-01-04
Filing date: 2019-01-04
Publication date: 2020-07-07
Anticipated expiration: 2039-01-04
Also published as: CN109680310A

Abstract

The invention relates to the technical field of electroplating, in particular to a nickel-antimony electroplating solution and a preparation method thereof, wherein the electroplating solution contains boric acid, sodium hypophosphite, a complexing agent and a proper amount of water, and also contains nickel salt and antimony salt, and the components and the contents of the electroplating solution are 20-80g/L of boric acid, 10-80g/L of sodium hypophosphite, 10-80g/L of the complexing agent, 1-20g/L of nickel salt and 1-10g/L of antimony salt. The electroplating method is utilized to obtain a uniform nickel-antimony plating layer, which has beautiful color, high specific capacity and good stability of the electroplating solution.

Description

Nickel-antimony electroplating solution and preparation method thereof

Technical Field

The invention relates to the technical field of electroplating, in particular to a nickel-antimony electroplating solution and a preparation method thereof.

Background

The electroplating has the advantages of low cost, simple process, easy operation and the like, and is widely applied in life. The electroplated single metal is far from meeting the requirements of modernization on functional materials. Therefore, the electroplating multi-component alloy has been rapidly developed in recent years, has a wide variety of types and excellent material properties, and is widely applied to the magnetic industry, the energy field and the like.

The theoretical capacity of antimony is up to 660mAh/g, which is much higher than that of the current commercial carbon material, and antimony and nickel-antimony alloy are energy materials with good prospects. At present, the methods for preparing the nickel-antimony alloy mainly comprise a hydrothermal method, a crosslinking reaction method and the like, and the preparation methods have the defects of high cost, long reaction time, difficulty in large-scale production and application and the like. Therefore, the method for preparing the nickel-antimony alloy with high specific capacity by seeking the low-cost electrodeposition technology has important significance.

Disclosure of Invention

The invention aims to solve the problems and provides a nickel-antimony electroplating solution and a preparation method thereof. The electroplating solution does not contain corrosive substances, is safe and environment-friendly, has high chemical stability, simple and controllable preparation process and good stability.

In order to achieve the purpose, the invention adopts the following technical scheme:

the nickel-antimony electroplating solution contains boric acid, sodium hypophosphite, a complexing agent and a proper amount of water, and also contains nickel salt and antimony salt, wherein the components and the contents of the electroplating solution are 20-80g/L of boric acid, 10-80g/L of sodium hypophosphite, 10-80g/L of the complexing agent, 1-20g/L of nickel salt and 1-10g/L of antimony salt.

Furthermore, the components and the contents of the electroplating solution are 40g/L boric acid, 40g/L sodium hypophosphite, 60g/L complexing agent, 10g/L nickel salt and 4g/L antimony salt.

Further, the nickel salt is a sulfate or chloride.

Further, the antimony salt is antimony potassium tartrate or antimony chloride.

Further, the complexing agent is sodium acetate, ammonium acetate, citric acid or ethylene diamine tetraacetic acid.

Further, the pH value of the electroplating solution is 0.5-3.0.

Further, the working temperature of the electroplating solution is 10-50 ℃.

Furthermore, the electroplating solution also comprises additives, wherein the additives are tin tetrabromide and 4-dimethylamino pyridine, and the specific contents are 2-5g/L of tin tetrabromide and 3-8g/L of 4-dimethylamino pyridine. Because the electroplating solution is an alloy electroplating solution of nickel salt and antimony salt, the two substances are added, and the purposes of improving the stability of the electroplating solution in the storage process on one hand and improving the deposition uniformity and stability of the electroplating solution in the electroplating process on the other hand are achieved.

Further, the electroplating solution also comprises tartaric acid and sodium tartrate, wherein the contents of the tartaric acid and the sodium tartrate are respectively 1-2g/L and 0.5-1 g/L. The purpose is to ensure that the electroplating solution has a stable polarization curve and stable controllability in the electrodeposition process, thereby improving the uniform stability of the final product.

A preparation method of a nickel-antimony electroplating solution comprises the following steps:

(1) adding 20-80g of boric acid, 10-80g of sodium hypophosphite and 10-80g of complexing agent into deionized water, and stirring and dissolving to prepare a mixed solution;

(2) adjusting the pH of the mixed solution to 1.0-3.0 with acid;

(3) adding 1-20g of nickel salt and 1-10g of antimony salt into the mixed solution, stirring and dissolving, adding the rest of deionized water to a constant volume of 1L, and adjusting the pH value of the mixed solution to 0.5-3.0 to obtain the antimony electroplating solution.

Further, the acid in the step (2) is hydrochloric acid or sulfuric acid.

Compared with the prior art, the invention has the beneficial effects that: the electroplating method is utilized to obtain a uniform nickel-antimony plating layer, which has beautiful color, high specific capacity and good stability of the electroplating solution. The electroplating solution with the proportion has a stable polarization curve, and can be matched with simple operation to obtain a product with good and uniform performance repeatability.

Detailed Description

The technical solution of the present invention is further described below by means of specific examples.

The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.

Example 1:

the preparation method of the nickel-antimony electroplating solution comprises the following steps:

adding 20g of boric acid, 10g of sodium hypophosphite and 10g of complexing agent (sodium acetate) into deionized water, stirring and dissolving to prepare a mixed solution, adjusting the pH to 1.0 by using HCl, adding 1g of antimony potassium tartrate and 1g of nickel chloride into the mixed solution, stirring and dissolving, adding the rest of deionized water until the total volume is 1L, and adjusting the pH to 0.5 to obtain the nickel-antimony electroplating solution.

Example 2:

adding 80g of boric acid, 80g of sodium hypophosphite and 80g of complexing agent (ammonium acetate) into deionized water, stirring and dissolving to prepare a mixed solution, adjusting the pH to 3.0 by using HCl, adding 10g of antimony potassium tartrate and 20g of nickel sulfate into the mixed solution, stirring and dissolving, adding the rest of deionized water until the total volume is 1L, and adjusting the pH to 3.0 to obtain the nickel-antimony electroplating solution.

Example 3:

adding 40g of boric acid, 40g of sodium hypophosphite and 60g of complexing agent (sodium acetate) into deionized water, stirring and dissolving to prepare a mixed solution, adjusting the pH to 2.0 by using HCl, adding 4g of antimony potassium tartrate and 10g of nickel chloride into the mixed solution, stirring and dissolving, adding the rest of deionized water until the total volume is 1L, and adjusting the pH to 1.5 to obtain the nickel-antimony electroplating solution.

Example 4:

adding 60g of boric acid, 20g of sodium hypophosphite and 20g of complexing agent (citric acid) into deionized water, stirring and dissolving to prepare a mixed solution, adjusting the pH to 1.0 by using HCl, adding 6g of antimony potassium tartrate and 5g of nickel sulfate into the mixed solution, stirring and dissolving, adding the rest of deionized water until the total volume is 1L, and adjusting the pH to 1.0 to obtain the nickel-antimony electroplating solution.

Example 5:

adding 40g of boric acid, 60g of sodium hypophosphite and 40g of complexing agent (ethylene diamine tetraacetic acid) into deionized water, stirring and dissolving to prepare a mixed solution, adjusting the pH to 3.0 by using HCl, adding 6g of antimony potassium tartrate and 10g of nickel chloride into the mixed solution, stirring and dissolving, adding the rest of deionized water until the total volume is 1L, and adjusting the pH to 1.5 to obtain the nickel-antimony electroplating solution.

Example 6:

adding 40g of boric acid, 40g of sodium hypophosphite and 60g of complexing agent (citric acid) into deionized water, stirring and dissolving to prepare a mixed solution, adjusting the pH to 2.0 by using HCl, adding 4g of antimony potassium tartrate and 20g of nickel chloride into the mixed solution, stirring and dissolving, adding the rest of deionized water until the total volume is 1L, and adjusting the pH to 1.5 to obtain the nickel-antimony electroplating solution.

Example 7:

in addition to example 5, 2g/L of tin tetrabromide and 8g/L of 4-dimethylaminopyridine were added at the same time as boric acid.

Example 8:

5g/L of tin tetrabromide and 3g/L of 4-dimethylaminopyridine were added in the same manner as boric acid in example 6.

Example 9:

3g/L of tin tetrabromide and 5g/L of 4-dimethylaminopyridine are added on the basis of example 5, and 2g/L of tartaric acid and 1g/L of sodium tartrate are added at the same time, and the adding time is the same as that of boric acid.

Example 10:

in addition to example 6, 4g/L tin tetrabromide and 7 g/L4-dimethylaminopyridine were added, along with 1g/L tartaric acid and 0.5g/L sodium tartrate, at the same time as boric acid.

The nickel-antimony plating layers obtained in the embodiments 1-6 are uniform, beautiful in color and relatively high in specific capacity.

Examples 7 to 10 are further improvements in that since the plating solutions are based on nickel salts and antimony salts, the existing complexing agents do not improve the storage stability, and therefore it is necessary to modify the storage stability so as to reduce the influence of the storage time on the plating performance. Meanwhile, the electroplating solutions of examples 1 to 6 have a problem of relatively weak repeatability in process control, which puts more demands on the control accuracy of the process, and are particularly improved in order to improve controllability and stability of the plating solution deposition.

Examples 7 to 8 guarantee the stability of the storage performance, and examples 1 to 6 increase the difficulty of the process operation and reduce the stability of the plating performance when stored for a long time, and the plating performance is reduced by 3 to 10 percent after the long-time storage; in contrast, the improvement of examples 7 to 8 had little effect on the coating within one month. Examples 9-10 are more robust control of the process, resulting in less operational difficulties and better repeatability of the process with looser process runs.

On the other hand, the performance of the modified plating layer tends to be more stable, and the process is more controllable.

The results of the electrochemical performance tests on the coatings obtained in examples 1 to 6 are given in the following table:

item	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6
							Lithium storage capacity/(mA h g)^-1)	600.0	535.2	530.0	560.6	540.5	537.1

The results of the electrochemical performance tests on the coatings obtained in examples 7 to 10 are given in the following table:

item	Example 7	Example 8	Example 9	Example 10
					Lithium storage capacity/(mA h g)^-1)	568.4	571.9	608.3	610.1

As can be seen from the above table, the antimony plating layer obtained by using the electroplating solution of the invention has high specific capacity and shows good electrochemical performance.

The foregoing is considered as illustrative of the preferred embodiments of the invention and the technical principles employed. It will be understood by those skilled in the art that the present invention is not limited to the particular embodiments described herein, but is capable of various obvious changes, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the invention. Therefore, although the present invention has been described in greater detail by the above embodiments, the present invention is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present invention, and the scope of the present invention is determined by the scope of the appended claims.

Claims

1. The nickel-antimony electroplating solution contains boric acid, sodium hypophosphite, a complexing agent and a proper amount of water, and is characterized by also containing nickel salt, antimony salt, tin tetrabromide, 4-dimethylamino pyridine, tartaric acid and sodium tartrate, wherein the components and the contents of the components of the electroplating solution are 20-80g/L of boric acid, 10-80g/L of sodium hypophosphite, 10-80g/L of complexing agent, 1-20g/L of nickel salt, 1-10g/L of antimony salt, 2-5g/L of tin tetrabromide, 3-8g/L of 4-dimethylamino pyridine, 1-2g/L of tartaric acid and 0.5-1g/L of sodium tartrate; the complexing agent is sodium acetate, ammonium acetate, citric acid or ethylenediamine tetraacetic acid.

2. The nickel-antimony electroplating solution as claimed in claim 1, wherein the components and contents of the electroplating solution are 40g/L boric acid, 40g/L sodium hypophosphite, 60g/L complexing agent, 10g/L nickel salt and 4g/L antimony salt.

3. The nickel-antimony electroplating bath according to claim 1 or 2, wherein the antimony salt is antimony potassium tartrate or antimony chloride.

4. The nickel antimony electroplating solution as claimed in claim 1, wherein the pH of the electroplating solution is 0.5-3.0.

5. The nickel antimony plating solution as recited in claim 1 wherein the plating solution is operated at a temperature of 10 to 50 ℃.

6. The method for preparing a nickel-antimony electroplating solution as claimed in claim 1, comprising the steps of: (1) adding 20-80g of boric acid, 10-80g of sodium hypophosphite, 10-80g of complexing agent, 2-5g of tin tetrabromide, 3-8g of 4-dimethylaminopyridine, 1-2g of tartaric acid and 0.5-1g of sodium tartrate into deionized water, and stirring and dissolving to prepare a mixed solution; (2) adjusting the pH of the mixed solution to 1.0-3.0 with acid; (3) adding 1-20g of nickel salt and 1-10g of antimony salt into the mixed solution, stirring and dissolving, adding the rest of deionized water to a constant volume of 1L, and adjusting the pH value of the mixed solution to 0.5-3.0 to obtain the tin-antimony electroplating solution.

7. The method as claimed in claim 6, wherein the acid in step (2) is hydrochloric acid or sulfuric acid.