Zinc-antimony electroplating solution and preparation method thereof

Abstract

The present invention relates to the field of electroplating technology, and in particular to a method for preparing a zinc-antimony electroplating solution, wherein a zinc-antimony alloy is prepared by a step potential method. The electroplating solution comprises the following components in mass concentration: 20-80 g / L of boric acid, 10-80 g / L of sodium hypophosphite, 10-80 g / L of a complexing agent, 1-20 g / L of a zinc salt, 1-15 g / L of an antimony salt, and the remainder is deionized water. The electroplating solution has good stability, and the zinc-antimony coating obtained by electroplating with the electroplating solution has a black appearance, a flat and uniform surface, a good bonding force between the coating and a substrate, and is not easy to fall off, and has a high sodium storage capacity when used as an anode material for a sodium battery.

Description

Technical Field

[0001] The invention relates to the technical field of electroplating, in particular to a method for preparing a zinc-antimony electroplating solution and a zinc-antimony alloy, and belongs to the field of energy materials and material corrosion. Background Art

[0002] Electroplating has the advantages of simple process, low cost, easy operation and large-scale application, and is widely used in life. Electroplating of single metals is far from meeting the modern demand for functional materials. Therefore, electroplating of multi-element alloys has developed rapidly in recent years, with a wide variety and excellent material properties. It has been widely used in the magnetic industry, energy field, etc. The theoretical capacity of antimony is as high as 660mAh / g, which is much higher than the current commercial carbon materials. Antimony and zinc-antimony alloys are a class of energy materials with very good prospects. At the same time, zinc-antimony alloys are a medium-temperature thermoelectric material and corrosion-resistant material. At present, the methods for preparing zinc-antimony alloys mainly include smelting, mechanical alloying and magnetron sputtering, etc., and these preparation methods have the disadvantages of expensive equipment, high cost, complex operating conditions, high production environment requirements, and difficulty in large-scale production and application. For example, when preparing Zn4Sb3 by smelting, it is difficult to control the phase structure and morphology of the material due to the volatilization of zinc elements during the preparation process. The Zn-Sb alloy prepared by mechanical alloying has defects such as uneven particle composition and particle size, and easy surface oxidation. The Zn / Antimony thin films prepared by magnetron sputtering are not uniform.

[0003] When preparing zinc-antimony alloy by electrodeposition, the composition and structure of the film can be changed by changing the parameters such as electrolyte, substrate, pH, current density and voltage. Compared with magnetron sputtering, smelting and other methods, the electrodeposition method has simple equipment, simple preparation process, easy large-scale production, low operating conditions, and therefore low cost. Because of this, the electrodeposition method is highly valued. For example, Yamamoto H et al. obtained zinc-antimony alloy thin films by heavy electrodeposition in ethylene glycol organic solvent. The use of organic solvents during electrodeposition will cause certain environmental pollution and the operation process is complicated. Summary of the invention

[0004] The purpose of the present invention is to solve the above problems and provide a method for preparing a zinc-antimony electroplating solution and a zinc-antimony alloy. The electroplating solution does not contain corrosive substances, is safe and environmentally friendly, has high chemical stability, and has a simple and controllable preparation process and good stability. The zinc-antimony alloy deposited by the method has a stable structure, uniform distribution, is not easy to fall off, and has a high sodium storage capacity.

[0005] In order to achieve the above-mentioned object of the invention, the present invention adopts the following technical solutions:

[0006] A zinc-antimony electroplating solution comprises the following components in mass concentrations: 20-80 g / L of boric acid, 10-80 g / L of sodium hypophosphite, 10-80 g / L of a complexing agent, 1-20 g / L of a zinc salt, 1-15 g / L of an antimony salt, and the balance is deionized water.

[0007] A zinc-antimony alloy is prepared by a step potential deposition method.

[0008] Among them, the main salt is zinc salt and antimony salt, boric acid is a buffer, sodium hypophosphite is a conductive agent, and the complexing agent is used to complex metal ions and separate metals. According to the functions of each formula, this appropriate ion ratio formula is obtained through experiments.

[0009] Preferably, the electroplating solution comprises the following components in mass concentrations: 40 g / L boric acid, 40 g / L sodium hypophosphite, 60 g / L complexing agent, 1 g / L zinc salt, 10 g / L antimony salt, and the remainder is deionized water.

[0010] Preferably, the zinc salt is a sulfate or a chloride.

[0011] Preferably, the antimony salt is potassium antimony tartrate or antimony chloride.

[0012] Preferably, the complexing agent is glycine, ammonium acetate or citric acid.

[0013] Preferably, the pH value of the electroplating solution is 0.5-3.0.

[0014] Preferably, the working temperature of the electroplating solution is 10-50°C.

[0015] Preferably, the deposition potential is -1.5V to -3.5V, and the deposition time is 80s.

[0016] A method for preparing a nickel-antimony electroplating solution comprises the following steps:

[0017] (1) adding 20-80 g of boric acid, 10-80 g of sodium hypophosphite, and 10-80 g of a complexing agent to deionized water, stirring and dissolving to prepare a mixed solution;

[0018] (2) adjusting the pH of the mixture to 1.0-3.0 with an acid;

[0019] (3) Add 1-20 g of zinc salt and 1-10 g of antimony salt to the above mixed solution, stir to dissolve, then add the remaining amount of deionized water to make the volume 1 L, and adjust the pH of the mixed solution to 0.5-3.0 to obtain a zinc-antimony electroplating solution.

[0020] Preferably, the acid in step (2) is hydrochloric acid or sulfuric acid.

[0021] Compared with the prior art (ZL2019100079694, an antimony electroplating solution and its preparation method, and ZL2019100079904, a nickel antimony electroplating solution and its preparation method), the present invention has the following beneficial effects: a more uniform and porous zinc antimony coating is obtained by using the method, the morphology is controllable, the sodium storage capacity is high, and the cycle performance and rate performance are better. In addition, the stability of the electroplating solution is also very good. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is a SEM image of the zinc-antimony alloy prepared in Example 1;

[0023] Figure 2 is a SEM image of the zinc-antimony alloy prepared in Example 2;

[0024] Figure 3 is a SEM image of the zinc-antimony alloy prepared in Example 3;

[0025] Figure 4 is a SEM image of the zinc-antimony alloy prepared in Example 4;

[0026] Figure 5 is the EDS image of the zinc-antimony alloy prepared in Example 4;

[0027] Figure 6 is the electrochemical performance diagram of the zinc-antimony alloy prepared in Example 4;

[0028] Figure 7 This is the electrochemical performance diagram of the zinc-antimony alloy prepared in Comparative Example 1. DETAILED DESCRIPTION

[0029] The technical solution of the present invention is further described below through specific embodiments.

[0030] Unless otherwise specified, the raw materials used in the embodiments of the present invention are all commonly used raw materials in the art, and the methods used in the embodiments are all conventional methods in the art.

[0031] Embodiment 1:

[0032] A method for preparing a zinc-antimony electroplating solution is as follows:

[0033] Add 40g of boric acid, 40g of sodium hypophosphite, and 60g of complexing agent (ammonium acetate) to deionized water, stir and dissolve to make a mixed solution, adjust pH to 1.5 with HCl, add 15g of potassium antimony tartrate and 8g of zinc chloride to the mixed solution, stir and dissolve, add the remaining amount of deionized water to a total volume of 1L, adjust pH to 1.5, and obtain zinc antimony electroplating solution. Perform step deposition at -1.5V and 0V for 80s to prepare zinc antimony alloy.

[0034] Embodiment 2:

[0035] A method for preparing a zinc-antimony electroplating solution is as follows:

[0036] Add 40g of boric acid, 40g of sodium hypophosphite, and 60g of complexing agent (ammonium acetate) to deionized water, stir and dissolve to make a mixed solution, adjust pH to 1.5 with HCl, add 15g of potassium antimony tartrate and 8g of zinc chloride to the mixed solution, stir and dissolve, add the remaining amount of deionized water to a total volume of 1L, adjust pH to 1.5, and obtain zinc antimony electroplating solution. Perform step deposition at -2.5V and 0V for 80s to prepare zinc antimony alloy.

[0037] Embodiment 3:

[0038] A method for preparing a zinc-antimony electroplating solution is as follows:

[0039] Add 40g of boric acid, 40g of sodium hypophosphite, and 60g of complexing agent (ammonium acetate) to deionized water, stir and dissolve to make a mixed solution, adjust pH to 1.5 with HCl, add 15g of potassium antimony tartrate and 8g of zinc chloride to the mixed solution, stir and dissolve, add the remaining amount of deionized water to a total volume of 1L, adjust pH to 1.5, and obtain zinc antimony electroplating solution. Perform step deposition at -3.0V and 0V for 80s to prepare zinc antimony alloy.

[0040] Embodiment 4:

[0041] A method for preparing a zinc-antimony electroplating solution is as follows:

[0042] Add 40g of boric acid, 40g of sodium hypophosphite, and 60g of complexing agent (ammonium acetate) to deionized water, stir and dissolve to make a mixed solution, adjust pH to 1.5 with HCl, add 15g of potassium antimony tartrate and 8g of zinc chloride to the mixed solution, stir and dissolve, add the remaining amount of deionized water to a total volume of 1L, adjust pH to 1.5, and obtain zinc antimony electroplating solution. Perform step deposition at -3.5 and 0V for 80s to prepare zinc antimony alloy.

[0043] Comparative Example 1:

[0044] A method for preparing a zinc-antimony electroplating solution is as follows:

[0045] Add 40g of boric acid, 40g of sodium hypophosphite, and 60g of complexing agent (ammonium acetate) to deionized water, stir and dissolve to make a mixed solution, adjust pH to 1.5 with HCl, add 15g of potassium antimony tartrate and 8g of zinc chloride to the mixed solution, stir and dissolve, add the remaining amount of deionized water to a total volume of 1L, adjust pH to 1.5, and obtain zinc antimony electroplating solution. Perform step deposition at -5.0 and 0V for 80s to prepare zinc antimony alloy.

[0046] Comparative Example 2:

[0047] A method for preparing a zinc-antimony alloy is as follows:

[0048] The same components as those in Example 4 were selected in the zinc-antimony electroplating solution of Comparative Example 2, and the deposition voltage was directly selected to be -3.0 V, and the deposition was performed for 80 seconds to prepare a zinc-antimony alloy.

[0049] The test results of the coatings obtained by the electrochemical performance test of Examples 1-4 and 1-2 are as follows:

[0050] project Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 <![CDATA[Sodium storage capacity / (mAh g -1 )]]> 289 295 304 356 312 260

[0051] It can be seen from the above table that the zinc-antimony coating obtained by using the electroplating solution of the present invention as a negative electrode material for a sodium ion battery has a high specific capacity, excellent cycle performance and rate performance, and exhibits good electrochemical performance.

[0052] The present invention is not limited to the step potential method, but also includes other possible methods for implementing zinc-antimony alloy electrodeposition.

Claims

1. A zinc-antimony electroplating solution, characterized in that: The electroplating solution includes the following components in mass concentration: Boric acid 20-80g / L, sodium hypophosphite 10-80g / L, complexing agent 10-80g / L, zinc salt 1-20g / L, antimony salt 1-15g / L, the balance is deionized water; The preparation method of the zinc-antimony electroplating solution: (1) adding 20-80 g of boric acid, 10-80 g of sodium hypophosphite, and 10-80 g of a complexing agent to deionized water, stirring and dissolving to prepare a mixed solution; (2) adjusting the pH of the mixture to 1.0-3.0 with an acid; (3) adding 1-20 g of zinc salt and 1-10 g of antimony salt to the above mixed solution, stirring to dissolve, then adding the remaining amount of deionized water to make the volume 1 L, and adjusting the pH of the mixed solution to 0.5-3.0 to obtain a zinc-antimony electroplating solution; The zinc-antimony alloy is obtained by depositing the zinc-antimony electroplating solution, wherein the deposition method used is a step potential method, the potential is -3.5 V and 0 V, and the deposition time is 80 s; The working temperature of the electroplating solution is 10-50°C.

2. A zinc-antimony electroplating solution according to claim 1, characterized in that: The electroplating solution includes the following components in mass concentrations: 40 g / L boric acid, 40 g / L sodium hypophosphite, 60 g / L complexing agent, 10 g / L zinc salt, 4 g / L antimony salt, and the balance is deionized water.

3. A zinc-antimony electroplating solution according to claim 1 or 2, characterized in that: The zinc salt is a sulfate or a chloride.

4. A zinc-antimony electroplating solution according to claim 1 or 2, characterized in that: The antimony salt is potassium antimony tartrate or antimony chloride.

5. A zinc-antimony electroplating solution according to claim 1 or 2, characterized in that: The complexing agent is glycine, ammonium acetate or citric acid.

6. A zinc-antimony electroplating solution according to claim 1 or 2, characterized in that: The pH value of the electroplating solution is 0.5-3.

0.

7. The method for preparing a zinc-antimony electroplating solution according to claim 1, characterized in that: The acid in step (2) is hydrochloric acid or sulfuric acid.

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