Compound dispersing agent, mixed electroplating solution and use

Abstract

Disclosed in the present application are a compound dispersing agent, a mixed electroplating solution and the use. The compound dispersing agent comprises a first anionic surfactant, a second anionic surfactant and a nonionic surfactant, the first anionic surfactant comprising a sulfonate compound, and / or the second anionic surfactant comprising one or more of betaine or carboxylate, and / or the nonionic surfactant comprising one or more of a sulfonic acid naphthoquinone formaldehyde condensate, a melamine-formaldehyde condensate and a methylnaphthalene sulfonic acid formaldehyde condensate sodium salt.

Description

Compound dispersants, mixed electroplating solutions and their applications

[0001] Priority declaration

[0002] This application claims priority to the Chinese patent application filed with the China Patent Office on January 16, 2024, with application number 202410063874.5. The entire contents of the above application are incorporated by reference into this application. Technical Field

[0003] The present application relates to the field of electroplating technology, and more specifically, to a compound dispersant, a mixed electroplating solution and a conductor. Background Art

[0004] Graphene is a new type of two-dimensional nanomaterial. Its nanosheets are single-atomic-thick two-dimensional materials composed of sp2 hybridized carbon atoms. It is the thinnest and hardest known nanomaterial, with a strength of up to 1.01 Tpa, 100 times that of structural steel, while its density is only one-fifth of that of structural steel. Graphene has a thermal conductivity of 5300 W / m·K, higher than carbon nanotubes and diamonds, and an electron mobility of over 200,000 cm at room temperature. 2 / V·S, higher than carbon nanotubes or silicon crystals, and a resistivity of only about 1Ω·m, lower than copper or silver, making it the lowest known resistivity material. Therefore, graphene is often used in composite electrical contact materials.

[0005] Metal-based graphene composite electrical contact materials offer superior electrical conductivity, wear resistance, and thermal conductivity compared to other reinforced composite electrical contact materials. Furthermore, graphene is highly stable, and dielectric corrosion is not a concern when composited with metal.

[0006] Due to its small size and large specific surface area, graphene is difficult to disperse. Furthermore, strong π-π interactions between graphene sheets cause single-layer graphene dispersed in a dispersion to easily aggregate, forming graphite, which severely impacts its performance. Surfactants and penetrants used in related electroplating solutions are difficult to disrupt the π-π interactions between graphene layers, and therefore fail to address the problem of single-layer graphene aggregation in a dispersion. Technical issues

[0007] The present application provides a compound dispersant, which aims to solve the problem in the related art that single-layer graphene dispersed in a dispersion liquid is prone to agglomeration. Technical Solutions

[0008] In a first aspect, the present application provides a compound dispersant,

[0009] The composite dispersant comprises a first anionic surfactant, a second anionic surfactant and a nonionic surfactant, wherein the first anionic surfactant comprises a sulfonate compound; and / or

[0010] The second anionic surfactant comprises one or more of betaine or carboxylate; and / or

[0011] The nonionic surfactant includes one or more of naphthoquinone sulfonate formaldehyde condensate, melamine-formaldehyde condensate, methylnaphthalene sulfonate formaldehyde condensate sodium salt, cresol sulfonate formaldehyde condensate sodium salt, and 2-naphthalene-sulfonate formaldehyde condensate sodium salt.

[0012] In a second aspect, the present application further provides a mixed electroplating solution comprising a compounded dispersant and water, wherein the compounded dispersant comprises the compounded dispersant described above. In a third aspect, the present application further provides a conductor comprising a substrate and a coating disposed externally of the substrate, wherein the coating is produced using the mixed electroplating solution described above. Beneficial effects

[0013] The beneficial effects of the present application are as follows: in the compound dispersant of the present application, the first anionic surfactant plays a role in surface wetting and dispersing, the second anionic surfactant plays a main dispersing role, and the nonionic surfactant plays a surface active wetting role. The compound dispersant of the present application has good synergistic coordination, plays a role in dispersing graphene in the plating solution system, and has a certain positive effect on the ion migration in the plating solution, and will not cause poisoning hazards to the plating solution. In addition, the compound dispersant of the present application also has a certain wetting effect on the cathode. Furthermore, the compound dispersant of the present application can make hydrogen bubbles easier to detach from the electroplated parts, thereby reducing the vacuum, and can wet the graphene, making it easier for the dispersant to play a role. Under the action of the dispersant, the graphene can repel and disperse from each other, which is convenient for electroplating. Modes for Carrying Out the Invention

[0014] In the description of this application, the term "including" means "including but not limited to".

[0015] The terms "multiple", "multiple times" or similar expressions refer to two (times) or more than two (times), for example, it can be two (times), three (times), four (times), five (times), six (times), etc.

[0016] The selection scope of the term "and / or" includes any one of two or more related listed items, and also includes any and all combinations of the related listed items, and the said any and all combinations include any two related listed items, any more related listed items, or the combination of all related listed items. For example, "A and / or B" includes three parallel solutions of A, B and A+B. For another example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, the technical solution connected by "logical OR"), and also includes any and all combinations of A, B, C, and D, that is, the combination of any two or any three of A, B, C, and D, and also includes the four-item combination of A, B, C, and D (that is, the technical solution connected by "logical AND").

[0017] The term "solid content" refers to the ratio of the mass of solid matter in the slurry to the total mass of the slurry.

[0018] The technical solution of this application is as follows:

[0019] In the first aspect, the present invention provides a composite dispersant, wherein the three components work together to effectively block or slow down the agglomeration of graphene in the dispersion, and the whole system has good stability. The composite dispersant comprises a first anionic surfactant, a second anionic surfactant and a nonionic surfactant, wherein:

[0020] In some embodiments, the first anionic surfactant may be selected from, but not limited to, sulfonate compounds.

[0021] In some embodiments, the second anionic surfactant includes one or more of a betaine or a carboxylate.

[0022] In some embodiments, the nonionic surfactant includes one or more of naphthoquinone sulfonate formaldehyde condensate, melamine-formaldehyde condensate, methylnaphthalene sulfonate formaldehyde condensate sodium salt, cresol sulfonate formaldehyde condensate sodium salt, and 2-naphthalene-sulfonate formaldehyde condensate sodium salt.

[0023] In the related art, although some dispersants can disperse graphene well in water, they cannot effectively disperse graphene in the plating solution. The plating solution is a solution system containing different ions and compounds. Different ions and compounds will have a certain impact on the dispersant added to the plating solution, which may cause the dispersant to lose its original dispersing function.

[0024] In the present application, the first anionic surfactant plays a role in surface wetting and dispersing, the second anionic surfactant plays a main dispersing role, and the non-ionic surfactant plays a surface active wetting role. The compound dispersant of the present application has good synergistic coordination, plays a role in dispersing graphene in the plating solution system, and has a certain positive effect on the ion migration in the plating solution, and will not cause poisoning hazards to the plating solution. In addition, the compound dispersant of the present application also has a certain wetting effect on the cathode. Furthermore, the compound dispersant of the present application can make hydrogen bubbles easier to detach from the electroplated parts, thereby reducing the vacuum, and can wet the graphene, making it easier for the dispersant to play a role. Under the action of the dispersant, the graphene can repel and disperse from each other, which is convenient for electroplating.

[0025] In some embodiments, the anionic surfactant includes a first anionic surfactant and a second anionic surfactant, and the mass ratio of the first anionic surfactant, the second anionic surfactant and the nonionic surfactant is (1-5):(0.5-4):(1-5), for example, 1:0.5:1, 1:2:3, 1:3:4, 1:4:5, 2:0.5:1, 2:1.5:2, 2:3:4, 2:4:5, 3:0.5:1, 3:1:2, 3:2:3, 3:3:4, 3:4:5, 4:0.5:1, 4:1:1, 4:2:2, 4:2:3, 4:3:4, 4:4:5, 5:0.5:1, 5:1:1, 5:2:2, 5:2:3, 5:3:4, 5:4:5, or a value between any two of the foregoing values. Within the range of the mass ratio, a compound dispersant that can effectively block or slow down the agglomeration of graphene in the dispersion can be obtained, and the compound dispersant system is stable.

[0026] In some embodiments, the first anionic surfactant may be selected from, but not limited to, sulfonate compounds.

[0027] The sulfonate compound can be selected from, but not limited to, one or more of alkyl sulfonates, methylene dinaphthalene sulfonates, alkylbenzene sulfonates, and alkylnaphthalene sulfonates.

[0028] The hydrocarbon sulfonate includes one or more of diheptyl sodium sulfosuccinate, dihexyl sodium sulfosuccinate and sodium dodecyl diphenyl ether disulfonate.

[0029] The methylene dinaphthalene sulfonate includes one or more of sodium methylene dinaphthalene sulfonate and potassium methylene dinaphthalene sulfonate.

[0030] The alkylbenzene sulfonate includes one or more of sodium xylene sulfonate, sodium toluene sulfonate, sodium cumene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, and calcium xylene sulfonate.

[0031] The alkylnaphthalene sulfonate includes one or more of sodium alkylnaphthalene sulfonate and sodium butylnaphthalene sulfonate.

[0032] In some embodiments, the second anionic surfactant includes one or more of a betaine or a carboxylate.

[0033] The betaines include trimethylglycine.

[0034] The carboxylates include one or more of alkyl carboxylates and amide polypeptide carboxylates.

[0035] The alkyl carboxylates include sodium stearate.

[0036] The amido polypeptide carboxylate includes sodium oleoamido polypeptide carboxylate.

[0037] In a second aspect, an embodiment of the present application further provides a mixed electroplating solution, which includes a compound dispersant, water, and graphene, wherein the compound dispersant includes the compound dispersant described in the first aspect above.

[0038] In some embodiments, the mixed electroplating solution further comprises stannate, copper salt, a complexing agent, and an alkali metal hydroxide.

[0039] The mixed electroplating solution of the present application improves the dispersibility of graphene in the copper-tin electroplating solution, so that the graphene after electroplating is evenly distributed on the plating layer and the copper-tin alloy is evenly distributed, thereby improving the conductivity and wear resistance of the plated parts.

[0040] In some embodiments, the mass concentration of the first anionic surfactant in the mixed electroplating solution is 1-5 g / L, for example, 1 g / L, 1.5 g / L, 2 g / L, 2.6 g / L, 3 g / L, 3.5 g / L, 4 g / L, 4.5 g / L, 5 g / L, or a value between any two of the foregoing values.

[0041] In some embodiments, the mass concentration of the second anionic surfactant in the mixed electroplating solution is 0.5-4 g / L, for example, 0.5 g / L, 0.8 g / L, 1 g / L, 1.2 g / L, 1.5 g / L, 1.8 g / L, 2 g / L, 2.5 g / L, 2.8 g / L, 3 g / L, 3.2 g / L, 3.5 g / L, 3.8 g / L, 4 g / L, or a value between any two of the foregoing values.

[0042] In some embodiments, the mass concentration of the nonionic surfactant in the mixed electroplating solution is 1-5 g / L, for example, 1 g / L, 1.2 g / L, 1.5 g / L, 1.8 g / L, 2 g / L, 2.2 g / L, 2.5 g / L, 2.8 g / L, 3 g / L, 3.3 g / L, 3.5 g / L, 3.8 g / L, 4 g / L, 4.2 g / L, 4.5 g / L, 4.8 g / L, 5 g / L, or a value between any two of the foregoing values.

[0043] In some embodiments, the mass volume concentration of the graphene in the mixed electroplating solution is 0.5-2 g / L, for example, 0.5 g / L, 0.8 g / L, 1 g / L, 1.2 g / L, 1.4 g / L, 1.6 g / L, 1.8 g / L, 2 g / L, or a value between any two of the foregoing values.

[0044] In some embodiments, the mass volume concentration of the stannate in the mixed electroplating solution is 85-130 g / L, for example, 85 g / L, 90 g / L, 95 g / L, 100 g / L, 105 g / L, 110 g / L, 115 g / L, 120 g / L, 125 g / L, 130 g / L, or a value between any two of the foregoing values.

[0045] In some embodiments, the copper salt in the mixed electroplating solution has a mass volume concentration of 5-20 g / L, for example, 5 g / L, 8 g / L, 10 g / L, 12 g / L, 15 g / L, 17 g / L, 18 g / L, 20 g / L, or a value between any two of the foregoing values.

[0046] In some embodiments, the mass volume concentration of the complexing agent in the mixed electroplating solution is 10-25 g / L, for example, 10 g / L, 12 g / L, 16 g / L, 18 g / L, 20 g / L, 22 g / L, 23 g / L, 25 g / L, or a value between any two of the foregoing values.

[0047] In some embodiments, the mass volume concentration of the alkali metal hydroxide in the mixed electroplating solution is 5-15 g / L, for example, 5 g / L, 8 g / L, 10 g / L, 12 g / L, 13 g / L, 15 g / L, or a value between any two of the foregoing values.

[0048] In some embodiments, the stannate includes one or more of sodium stannate and its hydrates. Preferably, the stannate includes sodium stannate trihydrate.

[0049] In some embodiments, the copper salt comprises cuprous cyanide.

[0050] In some embodiments, the complexing agent includes one or more of potassium cyanide and sodium cyanide.

[0051] In some embodiments, the alkali metal hydroxide includes one or more of potassium hydroxide and sodium hydroxide.

[0052] In some embodiments, the temperature of the mixed electroplating solution during electroplating is 45-65° C., for example, 45° C., 48° C., 50° C., 52° C., 54° C., 56° C., 58° C., 60° C., 64° C., 65° C., or a value between any two of the foregoing values.

[0053] In some embodiments, the current density of the mixed electroplating solution during electroplating is 0.5 to 1.5 A / dm 2 . For example, 0.5A / dm 2 , 0.6A / dm 2 , 0.8A / dm 2 , 1A / dm 2 , 1.2A / dm 2 , 1.3A / dm 2 , 1.5A / dm 2 .

[0054] In a third aspect, an embodiment of the present application further provides a conductor comprising a substrate and a plating layer located outside the substrate, wherein the plating layer is made from the mixed electroplating solution described in the second aspect above.

[0055] Example 1

[0056] This embodiment provides a compound dispersant, which is composed of distilled water, a first anionic surfactant, a second anionic surfactant and a nonionic surfactant; the first anionic surfactant is a sulfonate compound, the sulfonate compound is an alkyl sulfonate, and the alkyl sulfonate is sodium diheptyl sulfosuccinate; the second anionic surfactant is betaine, and the betaine is trimethylglycine; the nonionic surfactant is a sulfonic acid naphthoquinone formaldehyde condensate; in the compound dispersant, the mass fraction of the first anionic surfactant is 3%, the mass fraction of the second anionic surfactant is 2.25%, the mass fraction of the nonionic surfactant is 3%, and the balance is distilled water.

[0057] In this embodiment, the preparation method of the compound dispersant is prepared according to conventional methods in the art.

[0058] Example 2

[0059] This embodiment is basically the same as Example 1, except that, in the compound dispersant, the mass fraction of the first anionic surfactant is 1%, the mass fraction of the second anionic surfactant is 0.5%, the mass fraction of the nonionic surfactant is 1%, and the balance is distilled water.

[0060] Example 3

[0061] This embodiment is basically the same as Example 1, except that, in the compound dispersant, the mass fraction of the first anionic surfactant is 5%, the mass fraction of the second anionic surfactant is 4%, the mass fraction of the nonionic surfactant is 5%, and the balance is distilled water.

[0062] Example 4

[0063] This embodiment is basically the same as Example 1, except that the first anionic surfactant is a sulfonate compound, the sulfonate compound is an alkyl sulfonate, and the alkyl sulfonate is sodium dihexyl sulfosuccinate; the second anionic surfactant is a carboxylate, the carboxylate is an alkyl carboxylate, and the alkyl carboxylate is sodium stearate; and the nonionic surfactant is a melamine-formaldehyde condensate.

[0064] Example 5

[0065] This embodiment is basically the same as Example 1, except that the first anionic surfactant is a sulfonate compound, the sulfonate compound is an alkyl sulfonate, and the alkyl sulfonate is sodium dodecyl diphenyl ether disulfonate; the second anionic surfactant is a carboxylate, the carboxylate is an amide polypeptide carboxylate, and the amide polypeptide carboxylate is sodium oleamide polypeptide carboxylate; and the nonionic surfactant is a melamine-formaldehyde condensate.

[0066] Example 6

[0067] This embodiment is basically the same as Example 1, except that the first anionic surfactant is a sulfonate compound, the sulfonate compound is methylene dinaphthalene sulfonate, and the methylene dinaphthalene sulfonate is sodium methylene dinaphthalene sulfonate; the second anionic surfactant is a carboxylate, the carboxylate is an amide polypeptide carboxylate, and the amide polypeptide carboxylate is sodium oleamide polypeptide carboxylate; and the nonionic surfactant is sodium salt of methylnaphthalenesulfonic acid formaldehyde condensate.

[0068] Example 7

[0069] This embodiment is basically the same as Example 1, except that the first anionic surfactant is a sulfonate compound, the sulfonate compound is alkylbenzene sulfonate, and the alkylbenzene sulfonate is sodium xylene sulfonate; the second anionic surfactant is a carboxylate, the carboxylate is an alkyl carboxylate, and the alkyl carboxylate is sodium stearate; and the nonionic surfactant is sodium salt of cresol sulfonic acid formaldehyde condensate.

[0070] Example 8

[0071] This embodiment is basically the same as Example 1, except that the first anionic surfactant is a sulfonate compound, the sulfonate compound is alkylbenzene sulfonate, and the alkylbenzene sulfonate is ammonium xylene sulfonate; the second anionic surfactant is a carboxylate, the carboxylate is an amide polypeptide carboxylate, and the amide polypeptide carboxylate is sodium oleamide polypeptide carboxylate; and the nonionic surfactant is sodium salt of 2-naphthalenesulfonic acid formaldehyde condensate.

[0072] The following is an implementation of the mixed electroplating solution of the present application.

[0073] Electroplating solution example 1

[0074] The mixed electroplating solution of this embodiment includes a first anionic surfactant, a second anionic surfactant, a nonionic surfactant, water, graphene, a stannate, a copper salt, a complexing agent, and an alkali metal hydroxide. In the mixed electroplating solution, the first anionic surfactant is diheptyl sodium sulfosuccinate, and its content is 3 g / L, the second anionic surfactant is trimethylglycine, and its content is 2.25 g / L, the nonionic surfactant is naphthoquinone sulfonate formaldehyde condensate, and its content is 3 g / L. The mass volume concentration of the graphene is 1.25 g / L, the mass volume concentration of the stannate is 107 g / L, the mass volume concentration of the copper salt is 12 g / L, the mass volume concentration of the complexing agent is 17 g / L, and the mass volume concentration of the alkali metal hydroxide is 10 g / L. The stannate is sodium stannate trihydrate, the copper salt is cuprous cyanide, the complexing agent is potassium cyanide, and the alkali metal hydroxide is sodium hydroxide.

[0075] The mixed electroplating solution is prepared according to conventional methods in the art.

[0076] Electroplating solution example 2

[0077] This embodiment is basically the same as the electroplating solution embodiment 1, except that, in the mixed electroplating solution, the first anionic surfactant is diheptyl sodium sulfosuccinate, and its content is 1 g / L, the second anionic surfactant is trimethylglycine, and its content is 0.5 g / L, the nonionic surfactant is naphthoquinone sulfonate formaldehyde condensate, and its content is 1 g / L, the mass volume concentration of the graphene is 0.5 g / L, the mass volume concentration of the stannate is 85 g / L, the mass volume concentration of the copper salt is 5 g / L, the mass volume concentration of the complexing agent is 10 g / L, and the mass volume concentration of the alkali metal hydroxide is 5 g / L; the stannate is sodium stannate trihydrate, the copper salt is cuprous cyanide, the complexing agent is potassium cyanide, and the alkali metal hydroxide is potassium hydroxide.

[0078] Electroplating solution example 3

[0079] This embodiment is basically the same as the electroplating solution embodiment 1, except that, in the mixed electroplating solution, the first anionic surfactant is diheptyl sodium sulfosuccinate, and its content is 5 g / L, the second anionic surfactant is trimethylglycine, and its content is 4 g / L, the nonionic surfactant is naphthoquinone sulfonate formaldehyde condensate, and its content is 5 g / L, the mass volume concentration of the graphene is 2 g / L, the mass volume concentration of the stannate is 130 g / L, the mass volume concentration of the copper salt is 20 g / L, the mass volume concentration of the complexing agent is 25 g / L, and the mass volume concentration of the alkali metal hydroxide is 15 g / L; the stannate is sodium stannate trihydrate, the copper salt is cuprous cyanide, the complexing agent is sodium cyanide, and the alkali metal hydroxide is sodium hydroxide.

[0080] Electroplating solution example 4

[0081] The mixed electroplating solution of this embodiment comprises a first anionic surfactant, a second anionic surfactant, a nonionic surfactant, water, graphene, a stannate, a copper salt, a complexing agent, and an alkali metal hydroxide. In the mixed electroplating solution, the first anionic surfactant is sodium dihexyl sulfosuccinate, and its content is 3.5 g / L, the second anionic surfactant is sodium stearate, and its content is 2.5 g / L, the nonionic surfactant is melamine-formaldehyde condensate, and its content is 3.2 g / L, the mass volume concentration of the graphene is 0.8 g / L, the mass volume concentration of the stannate is 108 g / L, the mass volume concentration of the copper salt is 10 g / L, the mass volume concentration of the complexing agent is 15 g / L, and the mass volume concentration of the alkali metal hydroxide is 10 g / L; the stannate is sodium stannate trihydrate, the copper salt is cuprous cyanide, the complexing agent is potassium cyanide, and the alkali metal hydroxide is potassium hydroxide.

[0082] Electroplating solution example 5

[0083] The mixed electroplating solution of this embodiment comprises a first anionic surfactant, a second anionic surfactant, a nonionic surfactant, water, graphene, a stannate, a copper salt, a complexing agent, and an alkali metal hydroxide. In the mixed electroplating solution, the first anionic surfactant is sodium dodecyl diphenyl oxide disulfonate, with a content of 3 g / L, the second anionic surfactant is sodium oleamide polypeptide carboxylate, with a content of 2 g / L, and the nonionic surfactant is melamine-formaldehyde condensate, with a content of 3.5 g / L. The mass volume concentration of the graphene is 1 g / L, the mass volume concentration of the stannate is 102 g / L, the mass volume concentration of the copper salt is 12 g / L, the mass volume concentration of the complexing agent is 14 g / L, and the mass volume concentration of the alkali metal hydroxide is 9 g / L. The stannate is sodium stannate trihydrate, the copper salt is cuprous cyanide, the complexing agent is sodium cyanide, and the alkali metal hydroxide is sodium hydroxide.

[0084] Electroplating Solution Example 6

[0085] The mixed electroplating solution of this embodiment comprises a first anionic surfactant, a second anionic surfactant, a nonionic surfactant, water, graphene, a stannate, a copper salt, a complexing agent, and an alkali metal hydroxide. In the mixed electroplating solution, the first anionic surfactant is sodium methylene dinaphthalenesulfonate, with a content of 3 g / L, the second anionic surfactant is sodium oleamide polypeptide carboxylate, with a content of 2 g / L, and the nonionic surfactant is sodium salt of methylnaphthalenesulfonic acid formaldehyde condensate, with a content of 3.5 g / L. The mass volume concentration of the graphene is 0.8 g / L, the mass volume concentration of the stannate is 106 g / L, the mass volume concentration of the copper salt is 12 g / L, the mass volume concentration of the complexing agent is 13 g / L, and the mass volume concentration of the alkali metal hydroxide is 8 g / L. The stannate is sodium stannate trihydrate, the copper salt is cuprous cyanide, the complexing agent is sodium cyanide, and the alkali metal hydroxide is sodium hydroxide.

[0086] Electroplating solution example 7

[0087] The mixed electroplating solution of this embodiment comprises a first anionic surfactant, a second anionic surfactant, a nonionic surfactant, water, graphene, a stannate, a copper salt, a complexing agent, and an alkali metal hydroxide. In the mixed electroplating solution, the first anionic surfactant is sodium xylene sulfonate, and its content is 3.2 g / L, the second anionic surfactant is sodium stearate, and its content is 2.2 g / L, the nonionic surfactant is sodium salt of cresolsulfonic acid formaldehyde condensate, and its content is 2.8 g / L, the mass volume concentration of the graphene is 1.1 g / L, the mass volume concentration of the stannate is 108 g / L, the mass volume concentration of the copper salt is 10 g / L, the mass volume concentration of the complexing agent is 14 g / L, and the mass volume concentration of the alkali metal hydroxide is 10 g / L; the stannate is sodium stannate trihydrate, the copper salt is cuprous cyanide, the complexing agent is potassium cyanide, and the alkali metal hydroxide is potassium hydroxide.

[0088] Electroplating solution example 8

[0089] The mixed electroplating solution of this embodiment comprises a first anionic surfactant, a second anionic surfactant, a nonionic surfactant, water, graphene, a stannate, a copper salt, a complexing agent, and an alkali metal hydroxide. In the mixed electroplating solution, the first anionic surfactant is ammonium xylenesulfonate, with a content of 2.8 g / L, the second anionic surfactant is sodium oleamide polypeptide carboxylate, with a content of 2.5 g / L, and the nonionic surfactant is sodium salt of 2-naphthalenesulfonic acid formaldehyde condensate, with a content of 3.6 g / L. The mass volume concentration of the graphene is 1.2 g / L, the mass volume concentration of the stannate is 100 g / L, the mass volume concentration of the copper salt is 15 g / L, the mass volume concentration of the complexing agent is 16 g / L, and the mass volume concentration of the alkali metal hydroxide is 9 g / L. The stannate is sodium stannate trihydrate, the copper salt is cuprous cyanide, the complexing agent is potassium cyanide, and the alkali metal hydroxide is potassium hydroxide.

[0090] Comparative Example 1

[0091] Commercially available pure iron parts.

[0092] Comparative Example 2

[0093] This comparative example is basically the same as the electroplating solution example 1, except that the compound dispersant and graphene are removed from the mixed electroplating solution.

[0094] Comparative Example 3

[0095] This comparative example is basically the same as the electroplating solution example 1, except that the compound dispersant in the electroplating solution example 1 is replaced with 2-ethylhexyl sulfate sodium salt conventional in the art.

[0096] Comparative Example 4

[0097] This comparative example is basically the same as the electroplating solution example 1, except that the compound dispersant in the electroplating solution example 1 is replaced with dioctyl sodium sulfosuccinate conventional in the art.

[0098] The temperature during electroplating is 55°C and the current density is 1A / dm 2 After the electroplating is completed, the hardness test is carried out using Vickers silver hardness test. In order to eliminate the interference of the iron base metal on the coating hardness test, the thickness of the metal coating in the experimental test is greater than 30 microns; the microresistance is tested using a precision four-probe resistivity tester; the wear resistance test is carried out using a steel wool friction tester to detect the coating, measuring the mass before and after every 5000 frictions, and calculating the wear rate by the mass difference; the Zeta potential test method is the electrophoresis method, which measures the dispersion uniformity of the plating solution. The test results are shown in Table 1.

[0099] Table 1

[0100] Note: Wear resistance refers to the average number of times per micron, with the unit being / times.

[0101] As can be seen from Table 1, compared with comparative examples 3 and 4, the absolute values ​​of the Zeta potential of the electroplating solutions of Examples 1-8 of the present application are higher than those of Comparative Examples 3 and 4, indicating that the graphene dispersion in the electroplating solution to which the compound dispersant of the present application is added is better; the hardness of the products plated by Examples 1-8 of the present application is higher than that of Comparative Examples 1-4, indicating that the products plated by the electroplating solution with the compound dispersant of the present application have higher hardness; the microresistance of the products plated by Examples 1-8 of the present application is lower than that of Comparative Examples 1-4, indicating that the conductivity of the products plated by the electroplating solution with the compound dispersant of the present application is better; the average wear rate per 5000 times of the products plated by Examples 1-8 of the present application is lower than that of Comparative Examples 2-4, indicating that the wear resistance of the coating of the products plated by the electroplating solution with the compound dispersant of the present application is better. Since Comparative Example 1 is a pure iron part, Comparative Example 2 is only copper-tin plated, and Comparative Examples 3 and 4 are conventional dispersants in the art, the graphene dispersibility in the electroplating solutions of Comparative Examples 3 and 4 is worse than that of Examples 1-8.

Claims

1. A compound dispersant, the compound dispersant comprising a first anionic surfactant, a second anionic surfactant and a non-ionic surfactant, the first anionic surfactant comprising a sulfonate compound; and / or the second anionic surfactant comprising one or more of betaine or carboxylate; and / or the non-ionic surfactant comprising one or more of sulfonated naphthoquinone formaldehyde condensate, melamine-formaldehyde condensate, sodium salt of methylnaphthalenesulfonic acid formaldehyde condensate, sodium salt of cresolsulfonic acid formaldehyde condensate, sodium salt of 2-naphthalenesulfonic acid formaldehyde condensate.

2. The compound dispersant according to claim 1, wherein, The mass ratio of the first anionic surfactant, the second anionic surfactant and the non-ionic surfactant is (1 to 5):(0.5 to 4):(1 to 5).

3. The compound dispersant according to claim 1, wherein The sulfonate compound includes one or several of alkyl sulfonate, methylene bisnaphthalenesulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate; and / or The betaine includes trimethylglycine; and / or The carboxylate includes one or more of alkyl carboxylate, amide group polypeptide carboxylate.

4. The compound dispersant according to claim 3, wherein The alkyl sulfonate includes one or more of sodium diheptyl sulfosuccinate, sodium dihexyl sulfosuccinate, and sodium dodecyl diphenyl ether disulfonate; and / or The methylene bisnaphthalenesulfonate includes one or more of sodium methylene bisnaphthalenesulfonate or potassium methylene bisnaphthalenesulfonate; and / or The alkylbenzene sulfonate includes one or more of sodium xylene sulfonate, sodium toluene sulfonate, sodium isopropylbenzene sulfonate, potassium toluene sulfonate, ammonium xylene sulfonate, calcium xylene sulfonate; and / or The alkylnaphthalene sulfonate includes one or more of sodium alkylnaphthalene sulfonate and sodium butylnaphthalene sulfonate; and / or The alkyl carboxylate includes sodium stearate; and / or The amide group polypeptide carboxylate includes sodium oleoyl polypeptide carboxylate.

5. A mixed electroplating solution, the mixed electroplating solution comprising a compound dispersant, water, and graphene, wherein, The compound dispersant includes the compound dispersant according to any one of claims 1-4.

6. According to the mixed electroplating solution of claim 5, the mixed electroplating solution further includes stannate, copper salt, complexing agent and alkali metal hydroxide.

7. The mixed electroplating solution according to claim 6, wherein, In the mixed electroplating solution, the mass concentration of the first anionic surfactant is 1-5 g / L; and / or the mass concentration of the second anionic surfactant is 0.5-4 g / L; and / or the mass concentration of the non-ionic surfactant is 1-5 g / L and / or the mass concentration of the graphene is 0.5-2 g / L; and / or the mass concentration of the stannate is 85-130 g / L; and / or the mass concentration of the copper salt is 5-20 g / L; and / or the mass concentration of the complexing agent is 10-25 g / L; and / or the mass concentration of the alkali metal hydroxide is 5-15 g / L.

8. The mixed electroplating solution according to claim 6, wherein, In the mixed electroplating solution, the stannate includes one or more of sodium stannate and its hydrates; and / or the copper salt includes cuprous cyanide; and / or the complexing agent includes one or more of potassium cyanide and sodium cyanide; and / or the alkali metal hydroxide includes one or more of potassium hydroxide and sodium hydroxide.

9. The mixed electroplating solution according to claim 6, wherein, The temperature during electroplating of the mixed electroplating solution is 45 to 65 °C; and / or The current density is 0.5 to 1.5 A / dm 2 .

10. A conductor includes a substrate and a coating located outside the substrate, and the coating is prepared from the mixed electroplating solution according to any one of claims 5-9 above.

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