Composite plating solution, method for producing composite plating layer, and electrical contact material

Abstract

The present invention discloses a composite plating solution, a method for producing a composite plating layer, and an electrical contact material. The composite plating solution contains a water-soluble silver-containing compound, cyanide, graphene, a rare earth oxide, a dispersant, a wetting agent, and water, and the rare earth oxide includes at least one of lanthanum oxide, yttrium oxide, and cerium oxide. The present invention aims to solve the problem of resistance to hot-dip welding of conventional silver plating layers.

Description

[Technical Field]

[0001] The present invention claims priority to a Chinese patent application filed with the China Patent Office on November 18, 2022, bearing application number 202211447644.6 and entitled "Composite plating solution, method for manufacturing composite plating layer, and electrical contact material," the entire contents of which are incorporated herein by reference.

[0002] The present invention relates to an electroplating solution, and more particularly to a composite plating solution, a method for producing a composite plating layer, and an electrical contact material. [Background technology]

[0003] Electrical contact material is the core component and important material of an electrical switch, which is responsible for turning on and off the circuit and carrying the current load, and its performance determines the on / off ability and contact reliability of the electrical switch.

[0004] To ensure good electrical conductivity, electrical contact materials are usually plated with a silver layer on the surface of the substrate. Summary of the Invention [Problem to be solved by the invention]

[0005] The silver plating layer of the related art has low hardness and poor resistance to fusion welding, making it difficult to meet the actual needs of rapidly developing electrical equipment. [Means for solving the problem]

[0006] The present invention provides a composite plating solution, a method for producing a composite plating layer, and an electrical contact material that solve the problem of poor resistance to hot-dip welding of conventional silver plating layers.

[0007] In a first aspect, the present invention provides a composite plating solution, the composite plating solution comprising a water-soluble silver-containing compound, a cyanide, graphene, a rare earth oxide, a dispersant, a wetting agent, and water, wherein the rare earth oxide comprises at least one of lanthanum oxide, yttrium oxide, and cerium oxide.

[0008] Optionally, in some embodiments of the present invention, the weight ratio of the graphene to the rare earth oxide is 1:1.2-3.

[0009] Optionally, in some embodiments of the present invention, the particle size of the rare earth oxide is 10 to 120 nm.

[0010] Optionally, in some embodiments of the present invention, the rare earth oxides are yttrium oxide and lanthanum oxide, and the weight ratio of yttrium oxide to lanthanum oxide is 1:7-9.

[0011] Optionally, in some embodiments of the present invention, the rare earth oxides are yttrium oxide and cerium oxide, and the weight ratio of the yttrium oxide to the cerium oxide is 1:6-8.

[0012] Optionally, in some embodiments of the present invention, the rare earth oxides are yttrium oxide, cerium oxide, and lanthanum oxide, and the weight ratio of the yttrium oxide, the cerium oxide, and the lanthanum oxide is 1:1-1.5:5-8.

[0013] Optionally, in some embodiments of the present invention, the wetting agent comprises at least two of 1,3,6-naphthalenesulfonic acid sodium salt, lignin sulfonate, and alkyl sulfosuccinate salt.

[0014] Optionally, in some embodiments of the present invention, the dispersant includes at least one of naphtholsulfonic acid formaldehyde condensate sodium salt, naphthalenesulfonic acid sodium formaldehyde condensate, carboxylic acid-styrenesulfonic acid copolymer sodium salt, sodium dialkyl sulfosuccinate, sodium lauryl sulfate, and polyoxyethylene alkyl aryl ether.

[0015] Optionally, in some embodiments of the present invention, the concentration of silver ions in the composite plating solution is 5 to 10 g / L.

[0016] Optionally, in some embodiments of the present invention, the concentration of the graphene in the composite plating solution is 0.3 to 0.8 g / L.

[0017] Alternatively, in some embodiments of the present invention, the concentration of the rare earth oxide in the composite plating solution is 0.36 to 2.4 g / L.

[0018] Optionally, in some embodiments of the present invention, the concentration of the dispersant in the composite plating solution is 0.3 to 3.5 g / L.

[0019] Optionally, in some embodiments of the present invention, the concentration of the cyanide in the composite plating solution is 90 to 210 g / L, and / or The cyanide includes at least one of potassium cyanide and sodium cyanide.

[0020] Optionally, in some embodiments of the present invention, the concentration of the wetting agent in the composite plating solution is 0.3 to 2 g / L; and / or The pH of the composite plating solution is 7.5 to 10.5.

[0021] Optionally, in some embodiments of the present invention, the weight ratio of the wetting agent to the dispersing agent is 1:1-2.

[0022] Optionally, in some embodiments of the present invention, the composite plating solution comprises a water-soluble silver-containing compound, a cyanide, graphene, a rare earth oxide, a dispersant, a wetting agent, and water, and the rare earth oxide comprises at least one of lanthanum oxide, yttrium oxide, and cerium oxide; and / or In the composite plating solution, the silver ion concentration is 5 to 10 g / L, the graphene concentration is 0.3 to 0.8 g / L, the rare earth oxide concentration is 0.36 to 2.4 g / L, the wetting agent concentration is 0.3 to 2 g / L, the dispersant concentration is 0.3 to 3.5 g / L, and the cyanide concentration is 90 to 210 g / L. The composite plating solution has a pH of 7.5 to 10.5, and a weight ratio of the graphene to the rare earth oxide is 1:1.2 to 3.

[0023] In a second aspect, the present invention provides a method for producing a composite plating layer, the method comprising: providing a substrate and a composite plating solution as described above; and performing electroplating on the surface of the substrate using the composite plating solution to obtain a composite plating layer.

[0024] Optionally, in some embodiments of the present invention, the temperature of the composite plating solution is 16 to 24°C when the electroplating is performed.

[0025] Optionally, in some embodiments of the present invention, when the electroplating is performed, the current density is 0.3 to 0.7 A / dm 2 is.

[0026] In a third aspect, the present invention further provides an electrical contact material, the electrical contact material comprising a substrate and a composite plating layer coated on the surface of the substrate, the composite plating layer comprising the composite plating layer described above, or the composite plating layer being manufactured by the manufacturing method described above. [Effects of the Invention]

[0027] In the technical solution provided by the present invention, the composite plating solution contains a water-soluble silver-containing compound, cyanide, graphene, a rare earth oxide, a dispersant, a wetting agent, and water. By adding graphene and rare earth oxide, the composite plating layer produced with the composite plating solution not only has excellent electrical conductivity, abrasion resistance, hardness, and fusion welding resistance, but also reduces the amount of silver used and costs accordingly. The rare earth oxide includes at least one of lanthanum oxide, yttrium oxide, and cerium oxide. By selecting the rare earth oxide in accordance with the graphene and other components, the rare earth oxide can be stably present in the plating solution. The addition of a dispersant and a wetting agent helps the graphene and rare earth oxide to be dispersed stably and uniformly in the plating solution, fully demonstrating their respective excellent properties. [Brief explanation of the drawings]

[0028] In order to more clearly explain the technical solutions in the embodiments of the present invention, the following will briefly describe the drawings that need to be used in the description of the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention, and those skilled in the art can also obtain other drawings based on these drawings without any creative work. [Figure 1] FIG. 1 is a flowchart of a method for manufacturing a composite plating layer according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0029] Hereinafter, technical solutions in the embodiments of the present invention will be clearly and completely described with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments that can be obtained by those skilled in the art based on the embodiments of the present invention without creative effort fall within the scope of protection of the present invention. It should be understood that the specific embodiments described herein are merely for the purpose of explaining and interpreting the present invention, and do not limit the present invention. In the present invention, unless otherwise specified, directional terms used, such as "upper" and "lower," specifically refer to the drawing directions in the drawings. In addition, in the description of the present invention, the term "including" means "including but not limited to." It should be understood that various embodiments of the present invention may exist in a single range form, and the description in a single range form is merely for convenience and conciseness and should not be understood as limiting the scope of the present invention. For example, description of a range of 1 to 6 should be considered to have disclosed specific subranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., as well as single numbers within that range, such as 1, 2, 3, 4, 5, and 6, which are applicable to any range. Also, when describing numerical ranges herein, this includes any recited numbers (fractional or integer) within the stated range.

[0030] In the present invention, "and / or" describes a relationship between related objects and indicates that a three-way relationship may exist, for example, A and / or B may indicate that A exists alone, A and B exist simultaneously, or B exists alone, but A and B may be singular or plural.

[0031] In the present invention, "at least one" refers to one or more, and "plurality" refers to two or more. "At least one," "at least one of the following," or similar expressions refer to any combination of these terms, including any combination of single terms or multiple terms. For example, "at least one of a, b, or c," or "at least one of a, b, and c" can refer to a, b, c, a-b (i.e., a and b), a-c, bc, or a-bc, where a, b, and c can each be single or multiple.

[0032] An embodiment of the present invention provides a composite plating solution for producing a composite plating layer, the composite plating solution comprising a water-soluble silver-containing compound, cyanide, graphene, a rare earth oxide, a dispersant, a wetting agent, and water, wherein the rare earth oxide comprises at least one of lanthanum oxide, yttrium oxide, and cerium oxide.

[0033] The composite plating solution according to the present invention contains a water-soluble silver-containing compound, cyanide, graphene, a rare earth oxide, a dispersant, a wetting agent, and water. The graphene has excellent properties, such as high electrical conductivity, high thermal conductivity, high strength, high flexibility, and strong chemical inertness. The addition of graphene to the composite plating solution improves the arc-extinguishing properties, fusion welding resistance, abrasion resistance, and hardness of the composite plating layer. The addition of rare earth oxides contributes to improving the fusion welding resistance and hardness of the material. Overall, this composite plating solution combines excellent electrical conductivity, abrasion resistance, hardness, and fusion welding resistance, and the addition of highly conductive graphene reduces the amount of silver used and reduces costs.

[0034] Graphene has poor dispersibility and is prone to agglomeration in water, making it difficult to fully utilize its performance. Furthermore, composite plating solutions have poor stability, and each additional component reduces the stability of the plating solution, leading to phenomena such as decomposition and toxicity. To address these issues, the present invention carefully selects rare earth oxides to match the graphene and other components, ensuring that both graphene and rare earth oxides are stable in the plating solution. Meanwhile, the addition of dispersants and wetting agents helps ensure stable and uniform dispersion of graphene and rare earth oxides in the plating solution. During electroplating, the graphene deposits smoothly on the substrate surface, forming a uniformly distributed plating layer. This fully utilizes the excellent properties of the two materials, significantly improving the performance of the composite plating layer.

[0035] In some embodiments, the rare earth oxides are yttrium oxide and lanthanum oxide, and the weight ratio of the yttrium oxide to the lanthanum oxide is 1:7 to 1:9. For example, the weight ratio of the yttrium oxide to the lanthanum oxide may be 1:7, 1:7.2, 1:7.5, 1:8, 1:8.5, 1:8.7, 1:9, etc. By controlling the mixing ratio of the rare earth oxides, the rare earth oxides, graphene, and silver ions can be well matched, and the excellent performance of yttrium oxide and lanthanum oxide can be fully exerted while ensuring the stability of the composite plating solution, thereby improving the hardness and fusion welding resistance of the composite plating layer.

[0036] In some other embodiments, the rare earth oxides are yttrium oxide and cerium oxide, and the weight ratio of the yttrium oxide to the cerium oxide is 1:6 to 1:8. For example, the weight ratio of the yttrium oxide to the lanthanum oxide may be 1:6, 1:6.5, 1:7, 1:7.2, 1:7.5, 1:8, etc. By controlling the mixing ratio of the rare earth oxides, the rare earth oxides, graphene, and silver ions can be well matched, and the stability of the composite plating solution can be ensured, while the excellent performance of the yttrium oxide and cerium oxide can be fully exhibited, thereby improving the hardness and fusion welding resistance of the composite plating layer.

[0037] In still other embodiments, the rare earth oxides are yttrium oxide, cerium oxide, and lanthanum oxide, and the weight ratio of the yttrium oxide to the cerium oxide to the lanthanum oxide is 1:1 to 1.5:5 to 8. For example, the weight ratio of the yttrium oxide to the cerium oxide to the lanthanum oxide may be 1:1:5, 1:1.2:5, 1:1.5:5, 1:1:6, 1:1:7, 1:1:8, 1:1.5:6, 1:1.5:7, 1:1.5:8, etc. By controlling the mixing ratio of the rare earth oxides, the rare earth oxides, graphene, and silver ions are well matched, and the stability of the composite plating solution is ensured, while the excellent performance of the yttrium oxide, cerium oxide, and lanthanum oxide is fully exhibited, thereby improving the hardness and fusion welding resistance of the composite plating layer.

[0038] In some embodiments, the graphene concentration is 0.3 to 0.8 g / L, for example, 0.3 g / L, 0.5 g / L, 0.6 g / L, 0.7 g / L, 0.8 g / L, etc. The graphene concentration within this range contributes to an increase in the graphene content in the composite plating layer, and contributes to improvements in the performance of the plating layer, such as electrical conductivity, arc-extinguishing ability, fusion welding resistance, abrasion resistance, and hardness.

[0039] In some embodiments, the weight ratio of the graphene to the rare earth oxide is 1:1.2 to 3, for example, the weight ratio of the graphene to the rare earth oxide may be 1:1.2, 1:1.3, 1:1.5, 1:1.7, 1:2, 1:2.2, 1:2.5, 1:2.8, 1:3, etc. In this embodiment, blending the graphene and the rare earth oxide in an appropriate ratio contributes to ensuring the dispersibility of the graphene while also ensuring the uniform distribution of the graphene and the rare earth oxide in the plating layer. In some embodiments, the concentration of the rare earth oxide is 0.36 to 2.4 g / L, for example, 0.36 g / L, 0.4 g / L, 0.5 g / L, 0.8 g / L, 1 g / L, 1.5 g / L, 2 g / L, 2.2 g / L, 2.4 g / L, etc., and the concentration of the graphene in the composite plating solution may be 0.3 to 0.8 g / L. Controlling the ratio and concentration of graphene and rare earth oxide in the plating solution contributes to improving the transfer rate of graphene and rare earth oxide in the plating solution during electroplating, allowing the graphene and rare earth oxide to transfer quickly and at the same speed to the plating target area, ensuring uniform distribution of graphene and rare earth oxide in the plating layer, and achieving a balance that allows the graphene and rare earth oxide to fully exhibit their respective excellent performances in the plating layer, thereby ensuring electrical conductivity while improving performance such as hardness, fusion welding resistance, and abrasion resistance.

[0040] In some embodiments, the particle size of the rare earth oxide is 10 to 120 nm, and may be, for example, 10 to 20 nm, 20 to 50 nm, 40 to 60 nm, 60 to 80 nm, 80 to 100 nm, 100 to 120 nm, etc. Having the particle size within the above range contributes to the particles being uniformly distributed in the plating layer.

[0041] The addition of a wetting agent reduces the surface tension of graphene, helping it to bond with the dispersant, improving the dispersibility of graphene and preventing agglomeration. Furthermore, in some embodiments, the wetting agent includes at least two of 1,3,6-naphthalenesulfonic acid sodium salt, lignosulfonate, and alkylsulfosuccinate salt. Using any two or more of these wetting agents in combination can synergistically enhance the effect of improving the dispersibility of graphene. Specifically, the wetting agent used in the present technical proposal is a composite wetting agent containing at least two of the listed components. This composite wetting agent not only wets graphene to improve its surface wettability, but also acts synergistically to exfoliate previously aggregated graphene or multi-layer graphene. This effectively disperses graphene and reduces graphene aggregation, resulting in better dispersion and a longer dispersion time.

[0042] The dispersant includes at least one of naphtholsulfonic acid formaldehyde condensate sodium salt, sodium naphthalenesulfonate formaldehyde condensate, carboxylic acid-styrene sulfonic acid copolymer sodium salt, sodium dialkyl sulfosuccinate, sodium lauryl sulfate, and polyoxyethylene alkyl aryl ether. The addition of the dispersant contributes to improving the dispersion of graphene and rare earth oxides in the plating solution by working in conjunction with the wetting agent.

[0043] In some embodiments, the concentration of the wetting agent is 0.3 to 2 g / L, e.g., 0.3 g / L, 0.4 g / L, 0.5 g / L, 1 g / L, 1.5 g / L, 1.8 g / L, 2 g / L, etc. In other embodiments, the concentration of the dispersant is 0.3 to 3.5 g / L, e.g., 0.3 g / L, 0.4 g / L, 0.5 g / L, 1 g / L, 1.5 g / L, 1.8 g / L, 2 g / L, 3 g / L, 3.5 g / L, etc. Controlling the concentrations of the wetting agent and dispersant to be within the above ranges improves the dispersibility of each component in the plating solution, ensuring the stability of the plating solution and contributing to ensuring high migration rates of silver ions, rare earth oxides, and graphene in the plating solution.

[0044] In some embodiments, the weight ratio of the wetting agent to the dispersant is 1:1 to 1:2, for example, the weight ratio may be 1:1, 1:1.2, 1:1.3, 1:1.5, 1:1.7, 1:2, etc., thereby contributing to better synergy and cooperation between the wetting agent and the dispersant.

[0045] The cyanide may be any cyanide commonly used in the art, such as at least one selected from potassium cyanide and sodium cyanide.

[0046] In some embodiments, the cyanide has a concentration of 90 to 210 g / L, such as 90 g / L, 95 g / L, 100 g / L, 105 g / L, 110 g / L, 120 g / L, 130 g / L, 150 g / L, 160 g / L, 180 g / L, 200 g / L, 210 g / L, etc. Furthermore, in some embodiments, the cyanide is potassium cyanide, and the concentration of potassium cyanide in the composite plating solution may be 100 to 210 g / L.

[0047] In some embodiments, the water-soluble silver-containing compound may include silver nitrate. In the composite plating solution, the silver ion concentration is 5 to 10 g / L, for example, 5 g / L, 6 g / L, 7 g / L, 8 g / L, 9 g / L, 10 g / L, etc.

[0048] In some embodiments, the pH of the composite plating solution is 7.5 to 10.5, such as 7.5, 8, 8.5, 9, 10, or 10.5.

[0049] In a specific embodiment, the composite plating solution comprises a water-soluble silver-containing compound, cyanide, graphene, a rare earth oxide, a dispersant, a wetting agent, and water, and the rare earth oxide comprises at least one of lanthanum oxide, yttrium oxide, and cerium oxide.

[0050] In yet another embodiment, the composite plating solution contains 5-10 g / L of silver ions, 90-210 g / L of cyanide, 0.3-0.8 g / L of graphene, 0.36-2.4 g / L of rare earth oxide, 0.3-3.5 g / L of dispersant, 0.3-2 g / L of wetting agent, and water, the rare earth oxide being at least one of lanthanum oxide, yttrium oxide, and cerium oxide, the pH of the composite plating solution is 7.5-10.5, and the weight ratio of the graphene to the rare earth oxide is 1:1.2-3.

[0051] Based on the above embodiments, the present invention further provides a method for preparing the composite plating solution. Specifically, the method includes: dividing water into three portions; adding cyanide and a water-soluble silver-containing compound to one portion of the water and stirring to uniformly mix them to prepare a plating solution; adding a wetting agent to one portion of the water to prepare a wetting agent solution; and adding a dispersant to the remaining water to prepare a dispersant solution. While stirring, the wetting agent solution, the dispersant solution, graphene, and rare earth oxide are sequentially added to the plating solution, and the pH is adjusted to prepare a composite plating solution.

[0052] The present invention also provides a composite plating layer, which contains a rare earth oxide, graphene, and silver, and the rare earth oxide includes at least one of lanthanum oxide, yttrium oxide, and cerium oxide.

[0053] The composite plating layer according to the present invention contains a rare earth oxide, graphene, and silver. Graphene has excellent properties, such as high electrical conductivity, high thermal conductivity, high strength, high flexibility, and strong chemical inertness. The addition of graphene to the composite plating layer can improve the arc-extinguishing properties, fusion welding resistance, abrasion resistance, and hardness of the composite plating layer. The addition of rare earth oxide contributes to improving the fusion welding resistance and hardness of the composite plating layer. Overall, this composite plating layer has excellent electrical conductivity, abrasion resistance, hardness, and fusion welding resistance, and the addition of highly conductive graphene reduces the amount of silver used and reduces costs.

[0054] In some embodiments, the thickness of the composite plating layer is 25 to 40 μm.

[0055] In some embodiments, the weight ratio of the graphene to the rare earth oxide in the composite plating layer is 1:1.2-3.

[0056] In some embodiments, the rare earth oxide is a composition of yttrium oxide and lanthanum oxide in a weight ratio of 1:7-9; in some other embodiments, the rare earth oxide is a composition of yttrium oxide and cerium oxide in a weight ratio of 1:6-8; and in some other embodiments, the rare earth oxide is a composition of yttrium oxide, cerium oxide, and lanthanum oxide in a weight ratio of 1:1-1.5:5-8.

[0057] Furthermore, the method for producing a composite plating layer of the present invention includes the following steps, as shown in FIG.

[0058] In step S10, a substrate and the above-mentioned composite plating solution are provided.

[0059] In step S20, the surface of the substrate is electroplated using the composite plating solution to obtain a composite plating layer.

[0060] Here, the substrate may be any one of base materials prepared for plating with a plating film, and the material of the substrate may include, but is not limited to, at least one of copper, silver, gold, platinum, or an alloy thereof.

[0061] Here, the composite plating solution contains a water-soluble silver-containing compound, cyanide, graphene, a rare earth oxide, a dispersant, a wetting agent, and water, and the rare earth oxide includes at least one of lanthanum oxide, yttrium oxide, and cerium oxide.

[0062] In some embodiments, the temperature of the composite plating solution during electroplating is 16 to 24°C, for example, 16°C, 17°C, 18°C, 19°C, 20°C, 22°C, or 24°C. In other embodiments, the current density during electroplating is 0.3 to 0.7 A / dm 2 For example, 0.3A / dm 2 , 0.4A / dm 2 , 0.5A / dm 2 , 0.6A / dm 2 , 0.7A / dm 2 And so on.

[0063] The present invention also provides an electrical contact material comprising a substrate and a composite plating layer coated on the surface of the substrate, wherein the composite layer plating comprises the composite plating layer described above or is manufactured by the method for manufacturing a composite plating layer described above.

[0064] The technical solutions and technical effects of the present invention will be described in detail below through specific examples, comparative examples and experimental examples. The following examples are only some examples of the present invention and do not specifically limit the present invention.

[0065] Example 1 The composite plating solution contains silver nitrate, potassium cyanide, graphene, rare earth oxide, dispersant, wetting agent, and water. The silver ion concentration is 8 g / L, the graphene concentration is 0.6 g / L, the rare earth oxide concentration is 1.2 g / L, the wetting agent concentration is 0.3 g / L, the dispersant concentration is 0.3 g / L, and the potassium cyanide concentration is 105 g / L. The pH of the composite plating solution is 8.5. The rare earth oxides are yttrium oxide and lanthanum oxide, and the weight ratio of yttrium oxide to lanthanum oxide is 1:8. The particle size of the rare earth oxides ranges from 10 to 50 nm. The dispersant is a naphtholsulfonic acid-formaldehyde condensate sodium salt and a carboxylic acid-styrene sulfonic acid copolymer sodium salt in a weight ratio of 1:6. The wetting agent is 1,3,6-naphthalenesulfonic acid sodium salt, lignosulfonate, and alkylsulfosuccinate salt in a weight ratio of 7:2:1.

[0066] The composite plating solution was prepared as follows.

[0067] The water was divided into three portions, and potassium cyanide and silver nitrate were added to one portion of the water and stirred to mix uniformly to prepare a plating solution. A wetting agent was added to one portion of the water to prepare a wetting agent solution, and a dispersant was added to the remaining water to prepare a dispersant solution. While stirring, the wetting agent solution, dispersant solution, graphene, and rare earth oxide were added to the plating solution in that order, and the pH was adjusted to 8.5 to prepare a composite plating solution.

[0068] The electrical contact material is produced as follows.

[0069] A copper sheet was provided and placed in the composite plating solution prepared above, and a current density of 0.7 A / dm 2 The temperature of the electroplating (temperature of the composite plating solution) was set to 20° C., and electrodeposition was carried out to obtain a composite plating layer having a thickness of 30 μm.

[0070] Example 2 This example is basically the same as Example 1, with the only difference being that in this example, the rare earth oxides are replaced with yttrium oxide and lanthanum oxide, and the weight ratio of yttrium oxide to lanthanum oxide is 1:7.

[0071] Example 3 This example is basically the same as Example 1, with the only difference being that in this example, the rare earth oxides are replaced with yttrium oxide and lanthanum oxide, and the weight ratio of yttrium oxide to lanthanum oxide is 1:9.

[0072] Example 4 This example is basically the same as Example 1, with the only difference being that in this example, the rare earth oxides are replaced with yttrium oxide and cerium oxide, and the weight ratio of yttrium oxide to cerium oxide is 1:6.

[0073] Example 5 This example is basically the same as Example 1, with the only difference being that in this example, the rare earth oxides are replaced with yttrium oxide and cerium oxide, and the weight ratio of yttrium oxide to cerium oxide is 1:7.

[0074] Example 6 This example is basically the same as Example 1, with the only difference being that in this example, the rare earth oxides are replaced with yttrium oxide and cerium oxide, and the weight ratio of yttrium oxide to cerium oxide is 1:8.

[0075] Example 7 This example is basically the same as Example 1, with the only difference being that in this example, the rare earth oxides are replaced with yttrium oxide, cerium oxide, and lanthanum oxide, and the weight ratio of yttrium oxide, cerium oxide, and lanthanum oxide is 1:1:5.

[0076] Example 8 This example is basically the same as Example 1, with the only difference being that in this example, the rare earth oxides are replaced with yttrium oxide, cerium oxide, and lanthanum oxide, and the weight ratio of yttrium oxide to cerium oxide to lanthanum oxide is 1:1.2:6.

[0077] Example 9 This example is basically the same as Example 1, with the only difference being that in this example, the rare earth oxides are replaced with yttrium oxide, cerium oxide, and lanthanum oxide, and the weight ratio of yttrium oxide to cerium oxide to lanthanum oxide is 1:1.5:8.

[0078] Example 10 This example is basically the same as Example 1, with the only difference being that in this example, the rare earth oxides are replaced with cerium oxide and lanthanum oxide, and the weight ratio of yttrium oxide to lanthanum oxide is 1:7.

[0079] Example 11 This example is basically the same as Example 1, except that in this example, the concentration of graphene is changed from 0.6 g / L to 0.8 g / L and the concentration of rare earth oxide is changed from 1.2 g / L to 2.4 g / L.

[0080] Example 12 This example is basically the same as Example 1, except that in this example, the concentration of graphene is changed from 0.6 g / L to 0.3 g / L and the concentration of rare earth oxide is changed from 1.2 g / L to 0.36 g / L.

[0081] Example 13 This example is basically the same as Example 1, except that in this example, the wetting agent is replaced with a composition of 1,3,6-naphthalenesulfonic acid sodium salt and sodium dodecylbenzenesulfonate in a weight ratio of 1:1.

[0082] Example 14 This example is basically the same as Example 1, except that the wetting agent in this example is a composition of sodium dodecylbenzenesulfonate and lignin sulfonate in a weight ratio of 2:1, and the dispersant is a sodium naphthalenesulfonate formaldehyde condensate.

[0083] Example 15 This example is basically the same as Example 1, except that in this example, the concentration of the wetting agent is changed from 0.3 g / L to 1 g / L, the concentration of the dispersant is changed from 0.3 g / L to 2 g / L, and the dispersant is changed to a composition of sodium dialkyl sulfosuccinate, sodium lauryl sulfate, and polyoxyethylene alkyl aryl ether, with a weight ratio of 1:1:1.

[0084] Example 16 This example is basically the same as Example 1, except that in this example, the concentration of the wetting agent is changed from 0.3 g / L to 2 g / L, and the concentration of the dispersant is changed from 0.3 g / L to 3.5 g / L.

[0085] Example 17 This example is basically the same as Example 1, except that in this example, the silver ion concentration is changed from 8 g / L to 5 g / L, the pH of the composite plating solution is changed from 8.5 to 7.5, and the current density is changed to 0.7 A / dm when manufacturing the electrical contact material. 2 from 0.3A / dm 2 The only differences were that the temperature of the electroplating (temperature of the composite plating solution) was changed from 20°C to 16°C, and the thickness of the composite plating layer was changed from 30 μm to 25 μm.

[0086] Example 18 This example is basically the same as Example 1, with the only differences being that in this example, the potassium cyanide concentration is changed from 105 g / L to 210 g / L, the silver ion concentration is changed from 8 g / L to 10 g / L, the pH of the composite plating solution is changed from 8.5 to 10.5, when producing an electrical contact material, the electroplating temperature (temperature of the composite plating solution) is changed from 20 °C to 24 °C, and the thickness of the composite plating layer is changed from 30 μm to 40 μm.

[0087] Example 19 This embodiment is basically the same as the first embodiment, with the following differences: The composite plating solution contained silver nitrate, potassium cyanide, graphene, rare earth oxide, dispersant, wetting agent, and water. The silver ion concentration was 7 g / L, the graphene concentration was 0.3 g / L, the rare earth oxide concentration was 0.8 g / L, the wetting agent concentration was 0.3 g / L, the dispersant concentration was 0.3 g / L, and the potassium cyanide concentration was 100 g / L. The pH of the composite plating solution was 8.5. The rare earth oxide was lanthanum oxide, and the rare earth oxide particle size ranged from 100 to 120 nm. The dispersant was a 1:6 weight ratio of naphtholsulfonic acid-formaldehyde condensate sodium salt and a carboxylic acid-styrenesulfonic acid copolymer sodium salt. The wetting agent was a 7:2:1 weight ratio of 1,3,6-naphthalenesulfonic acid sodium salt, lignosulfonate, and alkyl sulfosuccinate salt.

[0088] The composite plating solution was prepared as follows.

[0089] The water was divided into three portions, and potassium cyanide and silver nitrate were added to one portion of the water and stirred to mix uniformly to prepare a plating solution. A wetting agent was added to one portion of the water to prepare a wetting agent solution, and a dispersant was added to the remaining water to prepare a dispersant solution. While stirring, the wetting agent solution, dispersant solution, graphene, and rare earth oxide were added to the plating solution in that order, and the pH was adjusted to 8.5 to prepare a composite plating solution.

[0090] The electrical contact material is produced as follows.

[0091] A copper sheet is provided and placed in the composite plating solution prepared above, and a current density of 0.6 A / dm 2 The electroplating temperature (temperature of the composite plating solution) was set to 20° C., and electrodeposition was carried out to obtain a composite plating layer having a thickness of 28 μm.

[0092] Comparative Example 1 This comparative example is basically the same as Example 1, except that, in this comparative example, the other components are the same except for the rare earth oxides.

[0093] Comparative Example 2 This comparative example is basically the same as Example 1, except that in this comparative example, the rare earth oxides were replaced with yttrium oxide, cerium oxide, and lanthanum oxide, and the weight ratio of yttrium oxide, cerium oxide, and lanthanum oxide was 1:1:9.

[0094] Comparative Example 3 This comparative example is basically the same as Example 1, except that in this comparative example, the rare earth oxides are replaced with yttrium oxide, cerium oxide, and lanthanum oxide, and the weight ratio of yttrium oxide, cerium oxide, and lanthanum oxide is 1:2:4.

[0095] Comparative Example 4 This comparative example was basically the same as Example 1, except that in this comparative example, the rare earth oxide was replaced with yttrium oxide and cerium oxide, and the weight ratio of yttrium oxide to cerium oxide was set to 1:9.

[0096] Comparative Example 5 This comparative example is basically the same as Example 1, except that in this comparative example, the rare earth oxides were replaced with yttrium oxide, cerium oxide, and scandium oxide, and the weight ratio of yttrium oxide, cerium oxide, and lanthanum oxide was 1:1:5.

[0097] Comparative Example 6 This comparative example was basically the same as Example 1, except that in this comparative example, the rare earth oxide was replaced with scandium oxide.

[0098] Comparative Example 7 This comparative example was basically the same as Example 1, except that the dispersant in this comparative example was replaced with sodium lauryl sulfate.

[0099] Comparative Example 8 This comparative example was basically the same as Example 1, except that the wetting agent in this comparative example was replaced with 1,3,6-naphthalenesulfonic acid sodium salt.

[0100] Comparative Example 9 This comparative example is basically the same as Example 1, except that in this comparative example, the other components are the same except for the wetting agent.

[0101] Comparative Example 10 This comparative example is basically the same as Example 1, except that in this comparative example, the other components are the same except for the dispersant.

[0102] Comparative Example 11 This comparative example is basically the same as Example 1, except that in this comparative example, the dispersant is replaced with byk-110, and the other components remain the same.

[0103] Comparative Example 12 This comparative example was basically the same as Example 1, except that in this comparative example, the concentration of rare earth oxide was changed from 1.2 g / L to 3 g / L.

[0104] Comparative Example 13 This comparative example is basically the same as Example 1, except that in this comparative example, the other components are the same except for graphene.

[0105] Comparative Example 14 This comparative example is basically the same as Example 1, except that in this comparative example, graphene, rare earth oxide, dispersant, and wetting agent were omitted.

[0106] Experimental Example 1 The zeta potentials of the composite plating solutions produced in Examples 1 to 18 and Comparative Examples 2 to 11 were measured, and the absolute values ​​of the measured zeta potentials are shown in Table 1.

[0107] [Table 1]

[0108] As can be seen from Table 1, compared to Comparative Examples 2 to 6, each Example had a higher absolute value of zeta potential, indicating that the composite plating solutions prepared in the Examples had better dispersibility and stability. This indicates that the present invention ensures compatibility of all components with the plating solution by adding at least one of yttrium oxide, cerium oxide, and lanthanum oxide as a rare earth oxide to the composite plating solution in a specific ratio, thereby ensuring the stability of the plating solution. Furthermore, compared to Comparative Example 12, Example 1 had higher dispersibility, indicating that adding a rare earth oxide such that the weight ratio of the graphene to the rare earth oxide was 1:1.2-3 contributes to improving the dispersibility of materials in the plating solution.

[0109] Compared with Comparative Examples 7 to 11, each Example had a higher absolute value of zeta potential, indicating that the composite plating solutions prepared in the Examples had better dispersibility and stability. This indicates that the present invention can achieve good synergistic effects between different dispersants and between a dispersant and a wetting agent by selecting a specific combination of dispersant and wetting agent, contributing to improved dispersibility and stability of the plating solution.

[0110] Experimental Example 2 The performance of the composite plating layers manufactured in Examples 1 to 19 and Comparative Examples 1, 12 to 14 was measured, including the abrasion resistance, fusion welding resistance, and hardness of the composite plating layers, and the results are shown in Table 2.

[0111] [Table 2-1] [Table 2-2]

[0112] As can be seen from Table 2, the composite plating layers prepared in Examples 1 to 19 all exhibited high hardness, abrasion resistance, and fusion welding resistance compared to Comparative Examples 1, 13, and 14, indicating that the composite plating solution provided by the present invention significantly improves the hardness, abrasion resistance, and fusion welding resistance of the plating layer by adding both graphene and rare earth oxides.

[0113] Comparing Examples 1 to 10 and 19, the composite plating layers produced in Examples 1 to 3 have higher hardness, abrasion resistance, and fusion welding resistance. This indicates that the addition of yttrium oxide and lanthanum oxide as rare earth oxides to the composite plating solution in the present invention ensures that all components are compatible with the plating solution, ensuring the stability of the plating solution while simultaneously effectively improving the hardness, abrasion resistance, and fusion welding resistance of the plating layer.

[0114] Comparing Example 1 with Comparative Example 12, it is found that Example 1 has better hardness, abrasion resistance, and fusion weld resistance than the Comparative Example, and that controlling the rare earth oxide content to within the range of 0.36 to 2.4 g / L not only improves the stability of the plating solution but also contributes to improving the overall performance of the plating layer.

[0115] The composite plating solution, the method for manufacturing a composite plating layer, and the electrical contact material according to the embodiments of the present invention have been described in detail above. Although the principles and embodiments of the present invention have been described using specific examples in this specification, the description of the above examples is merely intended to aid in understanding the method and concept of the present invention. Furthermore, those skilled in the art should understand that changes may be made in the specific embodiments and scope of application based on the concept of the present invention, and as such, the contents of this specification should not be construed as limiting the present invention.

Claims

1. a water-soluble silver-containing compound, a cyanide, graphene, a rare earth oxide, a dispersant, a wetting agent, and water, wherein the rare earth oxide includes at least one of lanthanum oxide, yttrium oxide, and cerium oxide; Composite plating solution.

2. the weight ratio of the graphene to the rare earth oxide is 1:1.2-3; The composite plating solution according to claim 1.

3. The particle size of the rare earth oxide is 10 to 120 nm. The composite plating solution according to claim 1 or 2.

4. the rare earth oxide is yttrium oxide and lanthanum oxide, and the weight ratio of the yttrium oxide to the lanthanum oxide is 1:7 to 1:9; The composite plating solution according to any one of claims 1 to 3.

5. the rare earth oxide is yttrium oxide and cerium oxide, and the weight ratio of the yttrium oxide to the cerium oxide is 1:6 to 1:8; The composite plating solution according to any one of claims 1 to 3.

6. the rare earth oxides are yttrium oxide, cerium oxide, and lanthanum oxide, and the weight ratio of the yttrium oxide, the cerium oxide, and the lanthanum oxide is 1:1 to 1.5:5 to 8; The composite plating solution according to any one of claims 1 to 3.

7. the wetting agent includes at least two of 1,3,6-naphthalenesulfonic acid sodium salt, ligninsulfonate, and alkylsulfosuccinate salt; The composite plating solution according to any one of claims 1 to 6.

8. the dispersant contains at least one of naphtholsulfonic acid formaldehyde condensate sodium salt, naphthalenesulfonic acid sodium formaldehyde condensate, carboxylic acid / styrenesulfonic acid copolymer sodium salt, dialkyl sodium sulfosuccinate, sodium lauryl sulfate, and polyoxyethylene alkyl aryl ether; The composite plating solution according to any one of claims 1 to 7.

9. In the composite plating solution, the concentration of silver ions is 5 to 10 g / L. The composite plating solution according to any one of claims 1 to 8.

10. In the composite plating solution, the concentration of the graphene is 0.3 to 0.8 g / L. The composite plating solution according to any one of claims 1 to 9.

11. 11. The composite plating solution according to claim 1, wherein the concentration of the rare earth oxide in the composite plating solution is 0.36 to 2.4 g / L.

12. In the composite plating solution, the concentration of the dispersant is 0.3 to 3.5 g / L. The composite plating solution according to any one of claims 1 to 11.

13. In the composite plating solution, the concentration of the cyanide is 90 to 210 g / L, and / or The cyanide includes at least one of potassium cyanide and sodium cyanide. The composite plating solution according to any one of claims 1 to 12.

14. In the composite plating solution, the concentration of the wetting agent is 0.3 to 2 g / L, and / or The pH of the composite plating solution is 7.5 to 10.

5. The composite plating solution according to any one of claims 1 to 13.

15. 15. The composite plating solution according to claim 1, wherein the weight ratio of the wetting agent to the dispersant in the composite plating solution is 1:1-2.

16. The composite plating solution comprises a water-soluble silver-containing compound, a cyanide, graphene, a rare earth oxide, a dispersant, a wetting agent, and water, and the rare earth oxide comprises at least one of lanthanum oxide, yttrium oxide, and cerium oxide; and / or In the composite plating solution, the silver ion concentration is 5 to 10 g / L, the graphene concentration is 0.3 to 0.8 g / L, the rare earth oxide concentration is 0.36 to 2.4 g / L, the wetting agent concentration is 0.3 to 2 g / L, the dispersant concentration is 0.3 to 3.5 g / L, the cyanide concentration is 90 to 210 g / L, the composite plating solution has a pH of 7.5 to 10.5, and the weight ratio of the graphene to the rare earth oxide is 1:1.2 to 3; The composite plating solution according to any one of claims 1 to 15.

17. A method for producing a composite plating layer, comprising: Providing a substrate and the composite plating solution according to any one of claims 1 to 16; and performing electroplating on the surface of the substrate using the composite plating solution to obtain a composite plating layer. Manufacturing method of composite plating layer.

18. When performing the electroplating, the temperature of the composite plating solution is 16 to 24°C. The method of claim 17.

19. When the electroplating is performed, the current density is 0.3 to 0.7 A / dm ２ That is, The method according to claim 17 or 18.

20. An electrical contact material, The plating method includes: a substrate; and a composite plating layer coated on a surface of the substrate; The composite plating layer is manufactured by the manufacturing method according to any one of claims 17 to 19. Electrical contact materials.

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