WO2022206923A1 - 复配型分散剂及制备方法、混合电镀液及制备方法 - Google Patents

复配型分散剂及制备方法、混合电镀液及制备方法 Download PDF

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WO2022206923A1
WO2022206923A1 PCT/CN2022/084617 CN2022084617W WO2022206923A1 WO 2022206923 A1 WO2022206923 A1 WO 2022206923A1 CN 2022084617 W CN2022084617 W CN 2022084617W WO 2022206923 A1 WO2022206923 A1 WO 2022206923A1
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compound
tween
mass fraction
dispersant
electroplating solution
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PCT/CN2022/084617
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English (en)
French (fr)
Inventor
胡益明
王川
林荣臻
吉燊
徐正利
周津裕
曾浪
申奇
林隽裕
郑建勇
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浙江正泰电器股份有限公司
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Priority to EP22779103.5A priority Critical patent/EP4227443A1/en
Priority to US18/252,829 priority patent/US20240003033A1/en
Priority to JP2023559818A priority patent/JP2024515483A/ja
Publication of WO2022206923A1 publication Critical patent/WO2022206923A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017—Mixtures of compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/46—Electroplating: Baths therefor from solutions of silver

Definitions

  • the invention relates to the technical field of materials, in particular to a compounded dispersant, a preparation method of the compounded dispersant, a mixed electroplating solution comprising the compounded dispersant, and a preparation method of the mixed electroplating solution.
  • Graphene is a two-dimensional crystalline material with excellent electrical, thermal and mechanical properties.
  • the thermal conductivity of single-layer graphene is as high as 5150W (m ⁇ K), and the carrier mobility reaches 15000cm2 (V ⁇ S); metal
  • the graphene-based composite electrical contact material has superior electrical conductivity, wear resistance and thermal conductivity than other reinforced phase composite electrical contact materials, and the graphene has good stability, and there is no dielectric corrosion after the graphene and metal are composited. The problem.
  • the object of the present invention is to overcome the defects of the prior art, and provide a compound dispersant, which can block or slow down the agglomeration of graphene in the dispersion; and also provides a compound dispersant preparation method, which is easy to operate;
  • a mixed electroplating solution comprising the compound type dispersant, wherein graphene dispersion is uniform and stable; and a method for preparing a mixed electroplating solution is provided, wherein the graphene distribution in the prepared mixed electroplating solution is uniform and stable.
  • a compound dispersant which is composed of distilled water, a nonionic surfactant, an anionic surfactant and a wetting agent; the nonionic surfactant is a Tween compound, and the anionic surfactant is Hydrocarbyl sulfonate compounds, wetting agents are amide compounds.
  • the wetting agent includes one or more of polyvinylpyrrolidone, alkylamide, lauric acid diethanolamide, sodium pyrrolidone carboxylate, polyoxyethylene alkylamide and alkylolamide.
  • the nonionic surfactant includes one or more of Tween-20, Tween-40, Tween-60 and Tween-80.
  • the anionic surfactants include sodium dihexyl succinate sulfonate, sodium lauryl succinate monoester sulfonate, sodium dodecyl diphenyl ether disulfonate, and monolauryl sulfosuccinate
  • disodium ester fatty alcohol polyoxyethylene ether (3) disodium sulfosuccinate monoester, dioctyl sodium sulfosuccinate and dioctyl sodium sulfosuccinate.
  • the mass fraction of nonionic surfactant is 1-10%.
  • the mass fraction of the wetting agent is 1-10%.
  • the mass fraction of anionic surfactant is 1-10%.
  • a method for preparing a compound dispersant comprising the following steps:
  • Step 1 add anionic surfactant and nonionic surfactant to distilled water with temperature T0, stirring time t0, 40°C ⁇ T0 ⁇ 60°C, 5 ⁇ t0 ⁇ 15min;
  • Step 2 adding a wetting agent to the mixture obtained in step 1, adding distilled water, stirring for time t1, to obtain a compound dispersant, 5min ⁇ t1 ⁇ 15min; in the compound type dispersant, the amount of the nonionic surfactant is The mass fraction is 1-10%, the mass fraction of anionic surfactant is 1-10%, the mass fraction of wetting agent is 1-10%, and the balance is distilled water.
  • the wetting agent includes one or more of polyvinylpyrrolidone, alkylamide, lauric acid diethanolamide, sodium pyrrolidone carboxylate, polyoxyethylene alkylamide and alkylolamide.
  • the nonionic surfactant includes one or more of Tween-20, Tween-40, Tween-60 and Tween-80.
  • the anionic surfactants include sodium dihexyl succinate sulfonate, sodium lauryl succinate monoester sulfonate, sodium dodecyl diphenyl ether disulfonate, and monolauryl sulfosuccinate
  • disodium ester fatty alcohol polyoxyethylene ether (3) disodium sulfosuccinate monoester, dioctyl sodium sulfosuccinate and dioctyl sodium sulfosuccinate.
  • a mixed electroplating solution includes the compound dispersant, a silver-based aqueous solution and graphene, and the silver-based aqueous solution includes KCN and silver ions.
  • the mass volume concentration of KCN is 90.0-200.0 g/L.
  • the mass volume concentration of silver ions is 15.0-50.0 g/L.
  • the mass volume concentration of graphene is 1.0-20.0 g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.5-0.7 A/dm 3 .
  • the rack plating current density of the mixed electroplating solution is 0.7-1.0 A/dm 3 .
  • the volume concentration of the compound dispersant is 15.0-45.0ml/L.
  • a method for preparing a mixed electroplating solution comprising the following steps:
  • Step 1 prepare a silver basic aqueous solution; in the silver basic aqueous solution, the mass volume concentration of KCN is 90.0-200.0 g/L, and the mass volume concentration of silver ions is 15.0-50.0 g/L;
  • Step 2 adding the compound dispersant and graphene into the silver basic aqueous solution in turn, stirring and mixing to obtain a mixed electroplating solution; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 15.0-45.0 ml/L, the mass volume concentration of graphene is 1.0-20.0 g/L.
  • the two compound dispersants of the present invention have synergistic components, and the lipophilic groups in the dispersants can be adsorbed on the surface of the graphene particles to form a surrounding layer, which can effectively block or slow down the agglomeration of graphene in the dispersion,
  • the hydrophilic group in the dispersant is combined with OH- ions in the water to ensure that the graphene is uniformly and stably dispersed in the dispersion.
  • the preparation method of the compound dispersant of the invention has simple operation, and the prepared compound dispersant can effectively block or slow down the agglomeration of graphene in the dispersion.
  • the mixed electroplating solution of the present invention the compound dispersant can effectively block or slow down the agglomeration of graphene, ensure that the graphene is stably and uniformly dispersed in the mixed electroplating solution, and is beneficial to improve the graphite in the silver-graphene electroplating layer of electroplating products.
  • the uniformity of graphene can better exert the electrical conductivity and wear resistance of graphene.
  • the graphene distribution is uniform and stable.
  • the specific embodiments of the compound dispersant and the preparation method of the present invention, the mixed electroplating solution including the compound dispersant and the preparation method are further described below with reference to the examples.
  • the compound dispersant and the preparation method of the present invention, the mixed electroplating solution including the compound dispersant and the preparation method are not limited to the descriptions of the following examples.
  • the invention discloses a compound dispersant, which is used for blocking or slowing down the agglomeration of graphene in a dispersion, which is composed of distilled water, nonionic surfactant, anionic surfactant and wetting agent;
  • the ionic surfactant is a Tween compound
  • the anionic surfactant is a hydrocarbyl sulfonate compound
  • the wetting agent is an amide compound.
  • the two compound dispersants of the present invention have synergistic components, and the lipophilic groups in the dispersants can be adsorbed on the surface of the graphene particles to form a surrounding layer, which can effectively block or slow down the agglomeration of graphene in the dispersion,
  • the hydrophilic group in the dispersant is combined with OH- ions in the water to ensure that the graphene is uniformly and stably dispersed in the dispersion.
  • the invention discloses a preparation method of a compound dispersant, which comprises the following steps:
  • Step 1 add anionic surfactant and nonionic surfactant to distilled water with temperature T0, stirring time t0, 5 ⁇ t0 ⁇ 15min, 40°C ⁇ T0 ⁇ 60°C;
  • step 2 the wetting agent is added to the mixture obtained in step 1, distilled water is added, and the stirring time is t1 to prepare a compound dispersant, 5min ⁇ t1 ⁇ 15min; in the compound dispersant, the nonionic surface active
  • the mass fraction of the agent is 1-10%
  • the mass fraction of the anionic surfactant is 1-10%
  • the mass fraction of the wetting agent is 1-10%
  • the balance is distilled water.
  • the preparation method of the compound dispersant of the invention has simple operation, and the prepared compound dispersant can effectively block or slow down the agglomeration of graphene in the dispersion.
  • the invention discloses a mixed electroplating solution, which comprises the compound dispersant, a silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions.
  • the mixed electroplating solution of the present invention the compound dispersant can effectively block or slow down the agglomeration of graphene, ensure that the graphene is stably and uniformly dispersed in the mixed electroplating solution, and is beneficial to improve the graphite in the silver-graphene electroplating layer of electroplating products.
  • the uniformity of graphene can better exert the electrical conductivity and wear resistance of graphene.
  • the invention discloses a method for preparing a mixed electroplating solution, which comprises the following steps:
  • Step 1 prepare a silver basic aqueous solution; in the silver basic aqueous solution, the mass volume concentration of KCN is 90.0-200.0 g/L, and the mass volume concentration of silver ions is 15.0-50.0 g/L;
  • Step 2 adding the compound dispersant and graphene into the silver basic aqueous solution in turn, stirring and mixing to obtain a mixed electroplating solution; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 15.0-45.0 ml/L, the mass volume concentration of graphene is 1.0-20.0 g/L.
  • the graphene distribution is uniform and stable.
  • the compound dispersant of the present invention is used to block or slow down the agglomeration of graphene in the dispersion liquid (such as the mixed electroplating solution of the present invention), which is composed of distilled water, nonionic surfactant, anionic surfactant and wetting agent Composition;
  • the non-ionic surfactant is a Tween compound,
  • the anionic surfactant is a hydrocarbyl sulfonate compound, and the wetting agent is an amide compound.
  • the anionic surfactants include sodium dihexyl succinate sulfonate, sodium lauryl succinate monoester sulfonate, sodium dodecyl diphenyl ether disulfonate, disodium lauryl sulfosuccinate monoester , fatty alcohol polyoxyethylene ether (3) one or more of disodium sulfosuccinate monoester, dioctyl sodium sulfosuccinate and dioctyl sodium sulfosuccinate.
  • the mass fraction of anionic surfactant is 1-10%.
  • the mass fraction of the anionic surfactant is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
  • the nonionic surfactant includes one or more of Tween-20, Tween-40, Tween-60 and Tween-80.
  • the mass fraction of nonionic surfactant is 1-10%.
  • the mass fraction of the nonionic surfactant is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
  • the wetting agent includes one or more of polyvinylpyrrolidone, alkylamide, lauric acid diethanolamide, sodium pyrrolidone carboxylate, polyoxyethylene alkylamide and alkylolamide.
  • the mass fraction of the wetting agent is 1-10%. Further, in the compound dispersant, the mass fraction of the wetting agent is 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
  • the preparation method of the compound dispersant of the present invention comprises the following operation steps:
  • Step 1 add anionic surfactant and nonionic surfactant to distilled water with temperature T0, stirring time t0, 40°C ⁇ T0 ⁇ 60°C, 5 ⁇ t0 ⁇ 15min.
  • T0 is 40°C, 45°C, 50°C, 55°C or 60°C.
  • t0 is 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min.
  • Step 2 adding a wetting agent to the mixture obtained in step 1, adding distilled water, stirring for time t1, to obtain a compound dispersant, 5min ⁇ t1 ⁇ 15min; in the compound type dispersant, the nonionic surfactant
  • the mass fraction of the anionic surfactant is 1-10%
  • the mass fraction of the anionic surfactant is 1-10%
  • the mass fraction of the wetting agent is 1-10%
  • the balance is distilled water.
  • t1 is 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min.
  • step 1 pre-prepared a compound dispersant with a mass of Mkg, and calculate the required mass of distilled water; step 1, take 15-45% of the required mass of distilled water and heat it to T0, add anionic surfactant and non-ionic surface active agent Active agent, stirring time t0; step 2, adding wetting agent to the mixture obtained in step 1, supplementing distilled water, stirring time t1, to prepare compound dispersant Mkg.
  • the compound dispersant is composed of sodium dihexyl succinate sulfonate, Tween-20, polyvinylpyrrolidone and distilled water; in the compound dispersant, the quality of sodium dihexyl succinate sulfonate is The fraction is 5%, the mass fraction of Tween-20 is 5%, the mass fraction of polyvinylpyrrolidone is 5%, and the balance is distilled water. Of course, due to raw materials and processes, it may also contain other impurities.
  • the preparation method of the compound dispersant comprises the following steps:
  • Step 1 into distilled water with a temperature of 50°C, sequentially add sodium dihexyl succinate sulfonate and Tween-20, and stir for 10min;
  • Step 2 adding polyvinylpyrrolidone to the mixture obtained in step 1, supplementing distilled water, and stirring for 10 minutes to obtain a compound dispersant; in the compound dispersant, the mass fraction of sodium dihexyl succinate sulfonate is 5%, the mass fraction of Tween-20 is 5%, the mass fraction of polyvinylpyrrolidone is 5%, and the balance is distilled water.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • the compound dispersant is composed of disodium lauryl sulfosuccinate monoester, Tween-20, polyoxyethylene alkylamide and distilled water;
  • the mass fraction of disodium ester is 5%, the mass fraction of Tween-20 is 5%, the mass fraction of polyoxyethylene alkylamide is 5%, and the balance is distilled water.
  • the preparation method of the compound dispersant comprises the following steps:
  • Step 1 into distilled water with a temperature of 50°C, add disodium lauryl sulfosuccinate monoester and Tween-20 in turn, and stir for 10min;
  • Step 2 adding polyoxyethylene alkyl amide to the mixture obtained in step 1, supplementing distilled water, and stirring for 10 min to obtain a compound dispersant; in the compound dispersant, lauryl sulfosuccinic acid monoester two
  • the mass fraction of sodium is 5%
  • the mass fraction of Tween-20 is 5%
  • the mass fraction of polyoxyethylene alkylamide is 5%
  • the balance is distilled water.
  • the compound dispersant is composed of sodium lauryl succinate monoester sulfonate, Tween-80, alkylamide and distilled water; in the compound type dispersant, the quality of sodium lauryl succinate monoester sulfonate is The fraction is 7%, the mass fraction of Tween-80 is 5%, the mass fraction of alkylamide is 4%, and the balance is distilled water.
  • the preparation method of the compound dispersant comprises the following steps:
  • Step 1 into distilled water with a temperature of 50°C, sequentially add sodium lauryl succinate monoester sulfonate and Tween-80, and stir for 10min;
  • Step 2 adding the alkylamide to the mixture obtained in step 1, and stirring for 10 minutes to obtain a compound dispersant; in the compound dispersant, the mass fraction of sodium lauryl succinate monoester sulfonate is 7% , the mass fraction of Tween-80 is 5%, the mass fraction of alkyl amide is 4%, and the balance is distilled water.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • the compound dispersant is composed of sodium dihexyl succinate sulfonate, Tween-60, sodium pyrrolidone carboxylate and distilled water; in the compound dispersant, sodium dihexyl succinate sulfonate
  • the preparation method of the compound dispersant comprises the following steps:
  • Step 1 into distilled water with a temperature of 50°C, sequentially add sodium dihexyl succinate sulfonate and Tween-60, and stir for 10min;
  • Step 2 adding sodium pyrrolidone carboxylate to the mixture obtained in step 1, supplementing distilled water, and stirring for 10 min to obtain a compound dispersant; in the compound dispersant, sodium dihexyl succinate sulfonate
  • the mass fraction is 6%
  • the mass fraction of Tween-60 is 5%
  • the mass fraction of sodium pyrrolidone carboxylate is 4%
  • the balance is distilled water.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • the compound dispersant is composed of sodium dodecyl dimethyl ether disulfonate, Tween-40, alkyl alcohol amide and distilled water;
  • the mass fraction of sodium sulfonate is 1%, the mass fraction of Tween-40 is 1%, the mass fraction of alkyl alcohol amide is 1%, and the balance is distilled water.
  • the preparation method of the compound dispersant comprises the following steps:
  • Step 1 into distilled water with a temperature of 40°C, add sodium dodecyl dimethyl ether disulfonate and Tween-40 in turn, and stir for 5min;
  • Step 2 adding the alkyl alcohol amide to the mixture obtained in step 1, adding distilled water, and stirring for 5 minutes to obtain a compound dispersant; in the compound dispersant, sodium dodecyl dimethyl ether disulfonate
  • the mass fraction is 1%
  • the mass fraction of Tween-40 is 1%
  • the mass fraction of alkyl alcohol amide is 1%
  • the balance is distilled water.
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • the compound dispersant is composed of fatty alcohol polyoxyethylene ether (3) disodium sulfosuccinate monoester, Tween-20, diethanolamide silicate and distilled water; in the compound dispersant, The mass fraction of fatty alcohol polyoxyethylene ether (3) disodium sulfosuccinate monoester is 10%, the mass fraction of Tween-20 is 10%, the mass fraction of silicate diethanolamide is 10%, and the balance is Distilled water.
  • the preparation method of the compound dispersant comprises the following steps:
  • Step 1 into distilled water at a temperature of 60° C., sequentially add fatty alcohol polyoxyethylene ether (3) disodium sulfosuccinate monoester and Tween-20, and stir for 15min;
  • Step 2 adding silicic acid diethanolamide to the mixture obtained in step 1, and stirring for 15 minutes to prepare a compound dispersant; in the compound dispersant, fatty alcohol polyoxyethylene ether (3) sulfosuccinic acid
  • fatty alcohol polyoxyethylene ether (3) sulfosuccinic acid The mass fraction of disodium monoester is 10%, the mass fraction of Tween-20 is 10%, the mass fraction of silicate diethanolamide is 10%, and the balance is distilled water.
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • the compound dispersant is composed of sodium dihexyl succinate sulfonate, sodium dodecyl dimethyl ether disulfonate, Tween-20, Tween-60, polyvinylpyrrolidone, sodium pyrrolidone carboxylate and Distilled water composition; in the compound dispersant, the mass fraction of sodium dihexyl succinate sulfonate is 4%, the mass fraction of sodium dodecyl dimethyl ether disulfonate is 3%, Tween-20 The mass fraction is 3%, the mass fraction of Tween-60 is 3%, the mass fraction of polyvinylpyrrolidone is 2%, the mass fraction of sodium pyrrolidone carboxylate is 2%, and the balance is distilled water.
  • the preparation method of the compound dispersant comprises the following steps:
  • Step 1 to the distilled water whose temperature is 45 °C, add anionic surfactant (sodium dihexyl succinate and sodium dodecyl dimethyl ether disulfonate), nonionic surfactant ( Tween-20 and Tween-60), stirring for 10min;
  • anionic surfactant sodium dihexyl succinate and sodium dodecyl dimethyl ether disulfonate
  • nonionic surfactant Tween-20 and Tween-60
  • Step 2 adding a wetting agent (polyvinylpyrrolidone and sodium pyrrolidone carboxylate) to the mixture obtained in step 1, adding distilled water, and stirring for 10 min to obtain a compound dispersant;
  • a wetting agent polyvinylpyrrolidone and sodium pyrrolidone carboxylate
  • the mass fraction of sodium dihexyl sulfonate is 4%
  • the mass fraction of sodium dodecyl dimethyl ether disulfonate is 3%
  • the mass fraction of Tween-20 is 3%
  • the mass fraction of Tween-60 The fraction is 3%
  • the mass fraction of polyvinylpyrrolidone is 2%
  • the mass fraction of sodium pyrrolidone carboxylate is 2%
  • the balance is distilled water.
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • the compound dispersant is composed of sodium dihexyl succinate sulfonate, disodium lauryl sulfosuccinate monoester, sodium lauryl succinate monoester sulfonate, Tween-20, Tween-80, Tween Wen-60, polyvinylpyrrolidone, polyoxyethylene alkylamide, alkylamide and distilled water; in the compound dispersant, the mass fraction of sodium dihexyl succinate sulfonate is 2%, lauryl sulfonate The mass fraction of disodium succinate monoester is 1%, the mass fraction of sodium lauryl succinate monoester sulfonate is 2%, the mass fraction of Tween-20 is 2%, and the mass fraction of Tween-80 is 2% %, the mass fraction of Tween-60 is 1%, the mass fraction of polyvinylpyrrolidone is 2%, the mass fraction of polyoxyethylene alkylamide is 2%, the mass fraction
  • the preparation method of the compound dispersant comprises the following steps:
  • Step 1 add anionic surfactants (sodium dihexyl succinate sulfonate, disodium lauryl sulfosuccinate monoester, and sodium lauryl succinate monoester sulfonate) into distilled water at a temperature of 55°C. ), nonionic surfactant (Tween-20, Tween-80 and Tween-60), stirred for 15min;
  • anionic surfactants sodium dihexyl succinate sulfonate, disodium lauryl sulfosuccinate monoester, and sodium lauryl succinate monoester sulfonate
  • Step 2 adding a wetting agent (polyvinylpyrrolidone, polyoxyethylene alkylamide and alkylamide) to the mixture obtained in step 1, supplementing distilled water, stirring for 15 min, and then preparing a compound dispersant;
  • a wetting agent polyvinylpyrrolidone, polyoxyethylene alkylamide and alkylamide
  • the mass fraction of sodium dihexyl succinate sulfonate is 2%
  • the mass fraction of disodium lauryl sulfosuccinate monoester is 1%
  • the mass fraction of sodium lauryl succinate monoester sulfonate is 1%.
  • the mass fraction of Tween-20 is 2%
  • the mass fraction of Tween-80 is 2%
  • the mass fraction of Tween-60 is 1%
  • the mass fraction of polyvinylpyrrolidone is 2%
  • the mass fraction of polyoxyethylene is 2%
  • the mass fraction of alkylamide is 2%
  • the mass fraction of alkylamide is 2%
  • the balance is distilled water.
  • the mixed electroplating solution of the present invention includes the compound dispersant, a silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions.
  • the mass volume concentration of KCN is 90.0-200.0 g/L.
  • the mass volume concentration of KCN is 90.0g/L, 100.0g/L, 110.0g/L, 120.0g/L, 130.0g/L, 140.0g/L, 150.0g/L , 160.0g/L, 170.0g/L, 180.0g/L, 190.0g/L or 200.0g/L.
  • the mass volume concentration of silver ions is 15.0-50.0 g/L.
  • the mass volume concentration of silver ions is 15.0g/L, 20.0g/L, 25.0g/L, 30.0g/L, 35.0g/L, 40.0g/L, 45.0g/L L or 50.0g/L.
  • the silver ions are provided by an aqueous solution prepared by electrolysis of a silver plate.
  • the mass volume concentration of graphene is 1.0-20.0 g/L.
  • the mass volume concentration of graphene is 1.0g/L, 1.5g/L, 2.0g/L, 2.5g/L, 3.0g/L, 4.0g/L, 5.0g/L L, 6.0g/L, 7.0g/L, 8.0g/L, 9.0g/L, 10.0g/L, 11.0g/L, 12.0g/L, 13.0g/L, 14.0g/L, 15.0g/ L, 16.0g/L, 17.0g/L, 18.0g/L, 19.0g/L or 20.0g/L.
  • the volume ratio concentration of the compound dispersant is 15-45ml/L. Further, in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 15ml/L, 20ml/L, 25ml/L, 30ml/L, 35ml/L, 40ml/L or 45ml/L.
  • the barrel plating current density of the mixed electroplating solution is 0.5-0.7 A/dm 2 .
  • the rolling current density of the mixed electroplating solution is 0.5A/dm 2 , 0.6A/dm 2 or 0.7A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 0.7-1.0 A/dm 2 . Further, the rack plating current density of the mixed electroplating solution is 0.7 A/dm 2 , 0.8 A/dm 2 , 0.9 A/dm 2 or 1.0 A/dm 2 .
  • the following is an embodiment of the method for preparing the mixed electroplating solution of the present invention.
  • Step 1 prepare a silver basic aqueous solution; in the silver basic aqueous solution, the mass volume concentration of KCN is 90-200 g/L, and the mass volume concentration of silver ions is 15-50 g/L.
  • Step 2 adding the compound dispersant and graphene into the silver basic aqueous solution in turn, and stirring and mixing to obtain a mixed electroplating solution; in the mixed electroplating solution, the volume concentration of the compound dispersant is 15-45ml /L, the mass volume concentration of graphene is 1.0-20g/L.
  • Embodiment 9 is a diagrammatic representation of Embodiment 9:
  • the mixed electroplating solution includes the composite dispersant of Embodiment 1, a silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the volume ratio concentration of the composite dispersant is 30.0 ml/L, the mass volume concentration of graphene is 2.0g/L; in the silver basic aqueous solution, the mass volume concentration of KCN is 150.0g/L, and the mass volume concentration of silver ions is 30.0g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.6 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 0.8 A/dm 2 .
  • the mixed electroplating solution includes the composite dispersant of Example 2, a silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the volume ratio concentration of the composite dispersant is 30.0 ml/L, the mass volume concentration of graphene is 2.0g/L; in the silver basic aqueous solution, the mass volume concentration of KCN is 150.0g/L, and the mass volume concentration of silver ions is 30.0g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.6 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 0.8 A/dm 2 .
  • the mixed electroplating solution includes the composite dispersant of Example 3, a silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the volume ratio concentration of the composite dispersant is 30.0 ml/L, the mass volume concentration of graphene is 2.0g/L; in the silver basic aqueous solution, the mass volume concentration of KCN is 150.0g/L, and the mass volume concentration of silver ions is 30.0g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.6 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 0.8 A/dm 2 .
  • Embodiment 12 is a diagrammatic representation of Embodiment 12
  • the mixed electroplating solution includes the composite dispersant of Example 4, a silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the volume ratio concentration of the composite dispersant is 30.0 ml/L, the mass volume concentration of graphene is 3.0g/L; in the silver basic aqueous solution, the mass volume concentration of KCN is 150.0g/L, and the mass volume concentration of silver ions is 30.0g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.6 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 0.8 A/dm 2 .
  • the mixed electroplating solution includes the composite dispersant of Embodiment 5, a silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the volume ratio concentration of the composite dispersant is 15.0 ml/L, the mass volume concentration of graphene is 1.0g/L; in the silver basic aqueous solution, the mass volume concentration of KCN is 90.0g/L, and the mass volume concentration of silver ions is 15.0g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.7 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 1.0 A/dm 2 .
  • the mixed electroplating solution includes the composite dispersant of Example 6, the silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the volume ratio concentration of the composite dispersant is 45.0 ml/L, the mass volume concentration of graphene is 20.0.0g/L; in the silver basic aqueous solution, the mass volume concentration of KCN is 200.0g/L, and the mass volume concentration of silver ions is 50.0g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.5A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 0.7A/dm 2 .
  • the mixed electroplating solution includes the composite dispersant of Embodiment 7, a silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the volume ratio concentration of the composite dispersant is 35.0 ml/L, the mass volume concentration of graphene is 10.0g/L; in the silver basic aqueous solution, the mass volume concentration of KCN is 180.0g/L, and the mass volume concentration of silver ions is 40g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.6 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 0.9 A/dm 2 .
  • the mixed electroplating solution includes the composite dispersant of Example 8, a silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the volume ratio concentration of the composite dispersant is 25.0 ml/L, the mass volume concentration of graphene is 5.0g/L; in the silver basic aqueous solution, the mass volume concentration of KCN is 130.0g/L, and the mass volume concentration of silver ions is 25.0g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.7 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 0.8 A/dm 2 .
  • the compound dispersant is composed of dioctyl sodium sulfosuccinate, Tween-40, Tween-60, polyvinylpyrrolidone and distilled water; in the compound dispersant, sulfosuccinic acid is The mass fraction of dioctyl sodium salt is 8%, the mass fraction of Tween-40 is 3%, the mass fraction of Tween-60 is 4%, the mass fraction of polyvinylpyrrolidone is 5%, and the balance is distilled water.
  • the preparation method of the compound dispersant comprises the following steps:
  • Step 1 add anionic surfactant (dioctyl sodium sulfosuccinate), nonionic surfactant (Tween-40 and Tween-60) to distilled water with a temperature of 50°C in turn, Stir for 13min;
  • anionic surfactant dioctyl sodium sulfosuccinate
  • nonionic surfactant Teween-40 and Tween-60
  • Step 2 adding a wetting agent (polyvinylpyrrolidone) to the mixture obtained in step 1, supplementing distilled water, stirring for 10 min, and then preparing a compound dispersant; in the compound dispersant, sulfosuccinic acid di
  • a wetting agent polyvinylpyrrolidone
  • sulfosuccinic acid di sulfosuccinic acid di
  • Embodiment 18 is a diagrammatic representation of Embodiment 18:
  • the compound dispersant is composed of dioctyl sodium sulfosuccinate, sodium dihexyl succinate sulfonate, Tween-20, polyvinylpyrrolidone, lauric acid diethanolamide and distilled water;
  • the mass fraction of dioctyl sodium sulfosuccinate is 2%
  • the mass fraction of dihexyl succinate sodium sulfonate is 1%
  • the mass fraction of Tween-20 is 3%
  • the mass fraction of polyvinylpyrrolidone is 2%.
  • the mass fraction is 1%
  • the lauric acid diethanolamide is 1%
  • the balance is distilled water.
  • the preparation method of the compound dispersant comprises the following steps:
  • Step 1 add anionic surfactant (dioctyl sodium sulfosuccinate and sodium dihexyl succinate sulfonate), nonionic surfactant (sodium sulfosuccinate) into distilled water with a temperature of 60°C. temperature-20), stirring for 15min;
  • anionic surfactant dioctyl sodium sulfosuccinate and sodium dihexyl succinate sulfonate
  • nonionic surfactant sodium sulfosuccinate
  • Step 2 adding a wetting agent (polyvinylpyrrolidone and lauric acid diethanolamide) to the mixture obtained in step 1, supplementing distilled water, stirring for 12 min, and then preparing a compound dispersant; in the compound dispersant,
  • a wetting agent polyvinylpyrrolidone and lauric acid diethanolamide
  • the mass fraction of dioctyl sodium sulfosuccinate is 2%
  • the mass fraction of dihexyl succinate sodium sulfonate is 1%
  • the mass fraction of Tween-20 is 3%
  • the mass fraction of polyvinylpyrrolidone is 1%
  • Lauric acid diethanolamide 1% the balance is distilled water.
  • the compound dispersant is composed of dioctyl sodium sulfosuccinate, disodium lauryl sulfosuccinate monoester, sodium dodecyl dimethyl ether disulfonate and dioctyl sodium sulfosuccinate.
  • Tween-20, Tween-60, Tween-80 polyvinylpyrrolidone, sodium lauric acid diethanolamide pyrrolidone base carboxylate, and distilled water;
  • the mass fraction of octyl sodium salt is 2%, the mass fraction of disodium lauryl sulfosuccinate monoester is 2%, the mass fraction of sodium dodecyl dimethyl ether disulfonate is 3%, and the mass fraction of dioctyl sulfonate
  • the mass fraction of sodium succinate is 2%, the mass fraction of Tween-20 is 2%, the mass fraction of Tween-60 is 5%, the mass fraction of Tween-80 is 2%, and the mass fraction of polyvinylpyrrolidone is 2%, the mass fraction of lauric acid diethanolamide is 3%, the mass fraction of sodium pyrrolidone carboxylate is 2%, and the balance is distilled water.
  • the preparation method of the compound dispersant comprises the following steps:
  • Step 1 add anionic surfactants (dioctyl sodium sulfosuccinate, disodium lauryl sulfosuccinate monoester, dodecyl dimethyl ether di- Sodium sulfonate and dioctyl sodium sulfosuccinate), nonionic surfactants (Tween-20, Tween-60 and Tween-80), stirred for 15min;
  • anionic surfactants dioctyl sodium sulfosuccinate, disodium lauryl sulfosuccinate monoester, dodecyl dimethyl ether di- Sodium sulfonate and dioctyl sodium sulfosuccinate
  • nonionic surfactants Teween-20, Tween-60 and Tween-80
  • Step 2 adding a wetting agent (polyvinylpyrrolidone, lauric acid diethanolamide and sodium pyrrolidone carboxylate) to the mixture obtained in step 1, supplementing distilled water, stirring for 15min, and then obtaining a compound dispersant;
  • a wetting agent polyvinylpyrrolidone, lauric acid diethanolamide and sodium pyrrolidone carboxylate
  • the mass fraction of dioctyl sodium sulfosuccinate is 2%
  • the mass fraction of disodium lauryl sulfosuccinate monoester is 2%
  • the mass fraction of dodecyl dimethyl ether disulfonic acid is 2%.
  • the mass fraction of sodium is 3%, the mass fraction of sodium dioctyl sulfosuccinate is 2%, the mass fraction of Tween-20 is 2%, the mass fraction of Tween-60 is 5%, and the mass fraction of Tween-80
  • the mass fraction is 2%, the mass fraction of polyvinylpyrrolidone is 2%, the lauric acid diethanolamide is 3%, the sodium pyrrolidone carboxylate is 2%, and the balance is distilled water.
  • Embodiment 20 is a diagrammatic representation of Embodiment 20.
  • the compound dispersant is composed of dioctyl sodium sulfosuccinate, Tween-40, Tween-60, alkyl alcohol amide, and distilled water; in the compound dispersant, dioctyl sulfonate
  • the mass fraction of sodium succinate is 5%
  • the mass fraction of Tween-40 is 2%
  • the mass fraction of Tween-60 is 3%
  • the mass fraction of alkyl alcohol amide is 5%
  • the balance is distilled water.
  • the preparation method of the compound dispersant comprises the following steps:
  • Step 1 add anionic surfactant (dioctyl sodium sulfosuccinate) and nonionic surfactant (Tween-40 and Tween-60) to the distilled water with a temperature of 50°C in turn, and stir for 12min ;
  • step 2 a wetting agent (alkyl alcohol amide) is added to the mixture obtained in step 1, distilled water is added, and stirred for 12 minutes, and a compound dispersant is obtained; in the compound dispersant, dioctyl sulfonation
  • the mass fraction of sodium succinate is 5%
  • the mass fraction of Tween-40 is 2%
  • the mass fraction of Tween-60 is 3%
  • the mass fraction of alkyl alcohol amide is 2%
  • the balance is distilled water.
  • Embodiment 21 is a diagrammatic representation of Embodiment 21.
  • the compound dispersant is composed of dioctyl sodium sulfosuccinate and dioctyl sodium sulfosuccinate, Tween-20 and Tween-40, polyoxyethylene alkylamide and lauric acid diethanolamide , and distilled water; in the compound dispersant, the mass fraction of dioctyl sodium sulfosuccinate is 5%, the mass fraction of dioctyl sodium sulfosuccinate is 5%, and the Tween-20 The mass fraction is 5%, the mass fraction of Tween-40 is 5%, the mass fraction of polyoxyethylene alkylamide is 6%, the mass fraction of lauric acid diethanolamide is 4%, and the balance is distilled water.
  • the preparation method of the compound dispersant comprises the following steps:
  • Step 1 add anionic surfactant (dioctyl sodium sulfosuccinate) and nonionic surfactant (Tween-40 and Tween-60) to the distilled water with a temperature of 60°C in turn, and stir for 12min ;
  • step 2 a wetting agent (alkyl alcohol amide) is added to the mixture obtained in step 1, distilled water is added, and stirred for 12 minutes, and a compound dispersant is obtained; in the compound dispersant, dioctyl sulfonation
  • the mass fraction of sodium succinate is 5%
  • the mass fraction of Tween-40 is 2%
  • the mass fraction of Tween-60 is 3%
  • the mass fraction of alkyl alcohol amide is 2%
  • the balance is distilled water.
  • the mixed electroplating solution includes the composite dispersant of Embodiment 17, a silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the volume ratio concentration of the composite dispersant is: 30.0ml/L, the mass volume concentration of graphene is 6.0g/L; in the silver basic aqueous solution, the mass volume concentration of KCN is 140.0g/L, and the mass volume concentration of silver ions is 35.0g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.7 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 0.8 A/dm 2 .
  • Embodiment 23 is a diagrammatic representation of Embodiment 23.
  • the mixed electroplating solution includes the composite dispersant of Embodiment 18, a silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the volume ratio concentration of the composite dispersant is: 40.0ml/L, the mass volume concentration of graphene is 4.0g/L; in the silver basic aqueous solution, the mass volume concentration of KCN is 100.0g/L, and the mass volume concentration of silver ions is 20.0g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.7 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 1.0 A/dm 2 .
  • Embodiment 24 is a diagrammatic representation of Embodiment 24.
  • the mixed electroplating solution includes the composite dispersant of Embodiment 19, the silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the volume ratio concentration of the composite dispersant is: 25.0ml/L, the mass volume concentration of graphene is 9.0g/L; in the silver basic aqueous solution, the mass volume concentration of KCN is 160.0g/L, and the mass volume concentration of silver ions is 45.0g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.6 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 0.7A/dm 2 .
  • Embodiment 25 is a diagrammatic representation of Embodiment 25.
  • the mixed electroplating solution includes the composite dispersant of Embodiment 20, a silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the volume ratio concentration of the composite dispersant is: 33.0ml/L, the mass volume concentration of graphene is 7.0g/L; in the silver basic aqueous solution, the mass volume concentration of KCN is 140.0g/L, and the mass volume concentration of silver ions is 40.0g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.6 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 0.8 A/dm 2 .
  • Embodiment 26 is a diagrammatic representation of Embodiment 26.
  • the mixed electroplating solution includes the composite dispersant of Embodiment 19, the silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the volume ratio concentration of the composite dispersant is: 17.0ml/L, the mass volume concentration of graphene is 10.0g/L; in the silver basic aqueous solution, the mass volume concentration of KCN is 190.0g/L, and the mass volume concentration of silver ions is 47.0g/L.
  • the barrel plating current density of the mixed electroplating solution is 0.5A/dm 2 .
  • the rack plating current density of the mixed electroplating solution is 0.7A/dm 2 .
  • the blank electroplating solution includes silver basic aqueous solution and graphene, and the silver basic aqueous solution includes KCN and silver ions; in the mixed electroplating solution, the mass volume concentration of graphene is 2.0 g/L; The mass volume concentration was 150.0 g/L, and the mass volume concentration of silver ions was 30.0 g/L.
  • the barrel plating current density of the blank plating solution is 0.6 A/dm 2 .
  • the rack plating current density of the blank plating solution is 0.8 A/dm 2 .
  • the mixed electroplating solution of the present invention is a graphene-silver mixed electroplating solution.
  • the electroplating product is electroplated through the following operations to form a graphene-silver mixed plating layer on the electroplating product. Specifically, the electroplating product is cleaned, and The cleaned product to be electroplated is put into potassium cyanide solution for cyanide activation, the activated product to be electroplated is pre-plated with silver, the pre-silvered product to be electroplated is put into a mixed electroplating solution for electroplating, and after the electroplating is completed, Wash the electroplated product multiple times.
  • Table 1 shows the physical parameters of the mixed electroplating solution and the blank electroplating solution (without adding the compound dispersant of the present invention) and the experimental data of the electroplating products of each embodiment (the larger the absolute value of the zeta potential value, the mixed electroplating).
  • the wear resistance is the average number of times it can withstand per micron, and the unit is /time.
  • the mixed electroplating solution of the present invention ensures that graphene is stably and uniformly distributed in the mixed electroplating solution, and can significantly improve the uniformity of graphene distribution in the silver-graphene coating, thereby significantly improving the product performance of electroplating products ( Including electrical conductivity, thermal conductivity, wear resistance, etc.).

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Abstract

本发明涉及材料技术领域，具体涉及一种复配型分散剂，其由蒸馏水、非离子型表面活性剂、阴离子型表面活性剂和润湿剂组成；所述非离子型表面活性剂为吐温类化合物，阴离子型表面活性剂为烃基磺酸盐类化合物，润湿剂为酰胺类化合物；所述复配型分散剂能阻断或减缓分散液中石墨烯的团聚。本发明还涉及一种复配型分散剂制备方法，用于制备所述复配型分散剂，其操作简单。本发明还涉及一种包括所述复配型分散剂的混合电镀液，其石墨烯分散均匀稳定。本发明还涉及一种混合电镀液制备方法，制得的混合电镀液中石墨烯分布均匀稳定。

Description

复配型分散剂及制备方法、混合电镀液及制备方法 技术领域
本发明涉及材料技术领域，具体涉及一种复配型分散剂，一种复配型分散剂制备方法，一种包括所述复配型分散剂的混合电镀液以及一种混合电镀液制备方法。
背景技术
石墨烯为一种二维晶体材料，具有优异的电学、热学以及机械性能，其中单层石墨烯热导率高达5150W(m·K)，载流子迁移率达到15000cm2(V·S)；金属基石墨烯复合电接触材料，具有比其他增强相复合电接触材料更有优越的导电性、耐磨性、导热性，而且石墨烯稳定性好，在石墨烯与金属复合后也不存在电介质腐蚀的问题。
石墨烯的片层之间有较强的π-π作用力，使得在分散液中分散的单层的石墨烯很容易发生团聚，重新形成石墨，严重影响了其性能；由于石墨烯疏水疏油的特殊结构，必须将通过添加特殊的表面活性剂和渗透剂才可以将其稳定的分散在水或其他溶剂中，以将石墨烯电镀在金属表面，获得金属基石墨烯复合电接触材料。
发明内容
本发明的目的在于克服现有技术的缺陷，提供一种复配型分散剂，能阻断或减缓分散液中石墨烯的团聚；还提供一种复配型分散剂制备方法，操作简单；还提供一种包括所述复配型分散剂的混合电镀液，其石墨烯分散均匀稳定；还提供一种混合电镀液制备方法，制得的混合电镀液中石墨烯分布均匀稳定。
为实现上述目的，本发明采用了如下技术方案：
一种复配型分散剂，其由蒸馏水、非离子型表面活性剂、阴离子型表 面活性剂和润湿剂组成；所述非离子型表面活性剂为吐温类化合物，阴离子型表面活性剂为烃基磺酸盐类化合物，润湿剂为酰胺类化合物。
优选的，所述润湿剂包括聚乙烯吡咯烷酮、烷基酰胺、月桂酸二乙醇酰胺、吡咯烷酮基羧酸钠、聚氧乙烯烷基酰胺和烷基醇酰胺中的一种或多种。
优选的，所述非离子型表面活性剂包括吐温-20、吐温-40、吐温-60和吐温-80中的一种或多种。
优选的，所述阴离子型表面活性剂包括丁二酸二己酯磺酸钠、月桂醇琥珀酸单酯磺酸钠、十二烷基二苯醚二磺酸钠、月桂基磺化琥珀酸单酯二钠、脂肪醇聚氧乙烯醚(3)磺基琥珀酸单酯二钠、磺基丁二酸二辛基钠盐和二辛基磺化琥珀酸钠中的一种或多种。
优选的，所述复配型分散剂中，非离子型表面活性剂的质量分数为1-10％。
优选的，所述复配型分散剂中，润湿剂的质量分数为1-10％。
优选的，所述复配型分散剂中，阴离子型表面活性剂的质量分数为1-10％。
一种复配型分散剂制备方法，其包括以下步骤：
步骤1，向温度为T0的蒸馏水中，加入阴离子型表面活性剂和非离子型表面活性剂，搅拌时间t0，40℃≤T0≤60℃，5≤t0≤15min；
步骤2，将润湿剂加入步骤1所得混合物中，补充蒸馏水，搅拌时间t1，得到复配型分散剂，5min≤t1≤15min；所述复配型分散剂中，非离子型表面活性剂的质量分数为1-10％，阴离子型表面活性剂的质量分数为1-10％，润湿剂的质量分数为1-10％，余量为蒸馏水。
优选的，所述润湿剂包括聚乙烯吡咯烷酮、烷基酰胺、月桂酸二乙醇酰胺、吡咯烷酮基羧酸钠、聚氧乙烯烷基酰胺和烷基醇酰胺中的一种或多种。
优选的，所述非离子型表面活性剂包括吐温-20、吐温-40、吐温-60和吐温-80中的一种或多种。
优选的，所述阴离子型表面活性剂包括丁二酸二己酯磺酸钠、月桂醇 琥珀酸单酯磺酸钠、十二烷基二苯醚二磺酸钠、月桂基磺化琥珀酸单酯二钠、脂肪醇聚氧乙烯醚(3)磺基琥珀酸单酯二钠、磺基丁二酸二辛基钠盐和二辛基磺化琥珀酸钠中的一种或多种。
一种混合电镀液，包括所述的复配型分散剂、银基础水溶液和石墨烯，银基水溶础液包括KCN和银离子。
优选的，所述银基础水溶液中，KCN的质量体积浓度为90.0-200.0g/L。
优选的，所述银基础水溶液中，银离子的质量体积浓度为15.0-50.0g/L。
优选的，所述混合电镀液中，石墨烯的质量体积浓度为1.0-20.0g/L。
优选的，所述混合电镀液的滚镀电流密度为0.5-0.7A/dm 3。
优选的，所述混合电镀液的挂镀电流密度为0.7-1.0A/dm 3。
优选的，所述混合电镀液中，复配型分散剂的体积比浓度为15.0-45.0ml/L。
一种混合电镀液制备方法，其包括以下步骤：
步骤1，制备银基础水溶液；所述银基础水溶液中，KCN的质量体积浓度为90.0-200.0g/L，银离子的质量体积浓度为15.0-50.0g/L；
步骤2，将所述的复配型分散剂和石墨烯依次加入银基础水溶液中，搅拌混合制得混合电镀液；所述混合电镀液中，复配型分散剂的体积比浓度为15.0-45.0ml/L，石墨烯的质量体积浓度为1.0-20.0g/L。
本发明的两种复配型分散剂，其各组分协同，分散剂中的亲油基团能吸附在石墨烯颗粒表面形成包围层，能有效阻断或减缓分散液中石墨烯的团聚，另外分散剂中的亲水基团与水中的OH-离子结合，保证石墨烯均匀、稳定的分散在分散液中。
本发明复配型分散剂制备方法，其操作简单，制得的复配型分散剂可有效阻断或减缓分散液中石墨烯的团聚。
本发明混合电镀液，其复配型分散剂能有效阻断或减缓石墨烯的团聚，保证石墨烯稳定均匀的分散在混合电镀液中，有利于提高电镀产品的银-石墨烯电镀层中石墨烯的均匀程度，更好的发挥石墨烯的导电、耐磨性能。
本发明混合电镀液制备方法，制备的混合电镀液中，石墨烯分布均匀稳定。
具体实施方式
以下结合实施例，进一步说明本发明的复配型分散剂及制备方法、包括所述复配型分散剂的混合电镀液及制备方法的具体实施方式。本发明的复配型分散剂及制备方法、包括所述复配型分散剂的混合电镀液及制备方法不限于以下实施例的描述。
本发明公开一种复配型分散剂，用于阻断或减缓分散液中石墨烯的团聚，其由蒸馏水、非离子型表面活性剂、阴离子型表面活性剂和润湿剂组成；所述非离子型表面活性剂为吐温类化合物，阴离子型表面活性剂为烃基磺酸盐类化合物，润湿剂为酰胺类化合物。
本发明的两种复配型分散剂，其各组分协同，分散剂中的亲油基团能吸附在石墨烯颗粒表面形成包围层，能有效阻断或减缓分散液中石墨烯的团聚，另外分散剂中的亲水基团与水中的OH-离子结合，保证石墨烯均匀、稳定的分散在分散液中。
本发明公开一种复配型分散剂制备方法，其包括以下步骤：
步骤1，向温度为T0的蒸馏水中，加入阴离子型表面活性剂和非离子型表面活性剂，搅拌时间t0，5≤t0≤15min，40℃≤T0≤60℃；
步骤2，将润湿剂加入步骤1中所得混合物中，补充蒸馏水，搅拌时间t1，制得复配型分散剂，5min≤t1≤15min；所述复配型分散剂中，非离子型表面活性剂的质量分数为1-10％，阴离子型表面活性剂的质量分数为1-10％，润湿剂的质量分数为1-10％，余量为蒸馏水。
本发明复配型分散剂制备方法，其操作简单，制得的复配型分散剂可有效阻断或减缓分散液中石墨烯的团聚。
本发明公开一种混合电镀液，其包括所述复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子。
本发明混合电镀液，其复配型分散剂能有效阻断或减缓石墨烯的团聚，保证石墨烯稳定均匀的分散在混合电镀液中，有利于提高电镀产品的银-石墨烯电镀层中石墨烯的均匀程度，更好的发挥石墨烯的导电、耐磨性能。
本发明公开一种混合电镀液制备方法，其包括以下步骤：
步骤1，制备银基础水溶液；所述银基础水溶液中，KCN的质量体积浓度为90.0-200.0g/L，银离子的质量体积浓度为15.0-50.0g/L；
步骤2，将所述的复配型分散剂和石墨烯依次加入银基础水溶液中，搅拌混合制得混合电镀液；所述混合电镀液中，复配型分散剂的体积比浓度为15.0-45.0ml/L，石墨烯的质量体积浓度为1.0-20.0g/L。
本发明混合电镀液制备方法，制备的混合电镀液中，石墨烯分布均匀稳定。
以下将结合具体实施例对本发明复配型分散剂以及复配型分散剂制备方法作进一步说明。
以下为本发明复配型分散剂的一种实施方式。
本发明复配型分散剂，用于阻断或减缓分散液(例如本发明混合电镀液)中石墨烯的团聚，其由蒸馏水、非离子型表面活性剂、阴离子型表面活性剂和润湿剂组成；所述非离子型表面活性剂为吐温类化合物，阴离子型表面活性剂为烃基磺酸盐类化合物，润湿剂为酰胺类化合物。
所述阴离子型表面活性剂包括丁二酸二己酯磺酸钠、月桂醇琥珀酸单酯磺酸钠、十二烷基二苯醚二磺酸钠、月桂基磺化琥珀酸单酯二钠、脂肪醇聚氧乙烯醚(3)磺基琥珀酸单酯二钠、磺基丁二酸二辛基钠盐和二辛基磺化琥珀酸钠中的一种或多种。
优选的，所述复配型分散剂中，阴离子型表面活性剂的质量分数为1-10％。所述复配型分散剂中，阴离子型表面活性剂的质量分数为1％、2％、3％、4％、5％、6％、7％、8％、9％或10％。
优选的，所述非离子型表面活性剂包括吐温-20、吐温-40、吐温-60和吐温-80中的一种或多种。
优选的，所述复配型分散剂中，非离子型表面活性剂的质量分数为1-10％。所述复配型分散剂中，非离子型表面活性剂的质量分数为1％、2％、3％、4％、5％、6％、7％、8％、9％或10％。
优选的，所述润湿剂包括聚乙烯吡咯烷酮、烷基酰胺、月桂酸二乙醇酰胺、吡咯烷酮基羧酸钠、聚氧乙烯烷基酰胺和烷基醇酰胺中的一种或多种。
优选的，所述复配型分散剂中，润湿剂的质量分数为1-10％。进一步的，所述复配型分散剂中，润湿剂的质量分数为1％、2％、3％、4％、5％、6％、7％、8％、9％或10％。
以下为本发明复配型分散剂制备方法的一种实施方式。
本发明复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为T0的蒸馏水中，加入阴离子型表面活性剂和非离子型表面活性剂，搅拌时间t0，40℃≤T0≤60℃，5≤t0≤15min。
优选的，T0为40℃、45℃、50℃、55℃或60℃。
优选的，t0为5min、6min、7min、8min、9min、10min、11min、12min、13min、14min或15min。
步骤2，将润湿剂加入步骤1中所得混合物中，补充蒸馏水，搅拌时间t1，得到复配型分散剂，5min≤t1≤15min；所述复配型分散剂中，非离子型表面活性剂的质量分数为1-10％，阴离子型表面活性剂的质量分数为1-10％，润湿剂的质量分数为1-10％，余量为蒸馏水。
优选的，t1为5min、6min、7min、8min、9min、10min、11min、12min、13min、14min或15min。
具体的，例如预配制质量为Mkg的复配型分散剂，计算蒸馏水所需质量；步骤1，取蒸馏水所需质量的15-45％加热至T0，加入阴离子型表面活性剂和非离子型表面活性剂，搅拌时间t0；步骤2，将润湿剂加入步骤1中所得混合物中，补充蒸馏水，搅拌时间t1，制得复配型分散剂Mkg。
实施例一：
所述复配型分散剂由丁二酸二己酯磺酸钠、吐温-20、聚乙烯吡咯烷酮和蒸馏水组成；所述复配型分散剂中，丁二酸二己酯磺酸钠的质量分数为5％，吐温-20的质量分数为5％，聚乙烯吡咯烷酮的质量分数为5％，余量为蒸馏水，当然由于原材料和工艺的原因，还可能含有其他杂质。
所述复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为50℃的蒸馏水中，依次加入丁二酸二己酯磺酸钠、吐温-20，搅拌10min；
步骤2，将聚乙烯吡咯烷酮加入步骤1得到的混合物中，补充蒸馏水， 搅拌10min后制得复配型分散剂；所述复配型分散剂中，丁二酸二己酯磺酸钠的质量分数为5％，吐温-20的质量分数为5％，聚乙烯吡咯烷酮的质量分数为5％，余量为蒸馏水。
实施例二：
所述复配型分散剂由月桂基磺化琥珀酸单酯二钠、吐温-20、聚氧乙烯烷基酰胺和蒸馏水组成；所述复配型分散剂中，月桂基磺化琥珀酸单酯二钠的质量分数为5％，吐温-20的质量分数为5％，聚氧乙烯烷基酰胺的质量分数为5％，余量为蒸馏水。
所述复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为50℃的蒸馏水中，依次加入月桂基磺化琥珀酸单酯二钠、吐温-20，搅拌10min；
步骤2，将聚氧乙烯烷基酰胺加入步骤1得到的混合物中，补充蒸馏水，搅拌10min后制得复配型分散剂；所述复配型分散剂中，月桂基磺化琥珀酸单酯二钠的质量分数为5％，吐温-20的质量分数为5％，聚氧乙烯烷基酰胺的质量分数为5％，余量为蒸馏水。
实施例三：
所述复配型分散剂由月桂醇琥珀酸单酯磺酸钠、吐温-80、烷基酰胺和蒸馏水组成；所述复配型分散剂中，月桂醇琥珀酸单酯磺酸钠的质量分数为7％，吐温-80的质量分数为5％，烷基酰胺的质量分数为4％，余量为蒸馏水。
所述复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为50℃的蒸馏水中，依次加入月桂醇琥珀酸单酯磺酸钠、吐温-80，搅拌10min；
步骤2，将烷基酰胺加入步骤1得到的混合物中，搅拌10min后制得复配型分散剂；所述复配型分散剂中，月桂醇琥珀酸单酯磺酸钠的质量分数为7％，吐温-80的质量分数为5％，烷基酰胺的质量分数为4％，余量为蒸馏水。
实施例四：
所述复配型分散剂由丁二酸二己酯磺酸钠、吐温-60、吡咯烷酮基羧酸 钠和蒸馏水组成；所述复配型分散剂中，丁二酸二己酯磺酸钠的质量分数6％，吐温-60的质量分数为5％，吡咯烷酮基羧酸钠的质量分数为4％，余量为蒸馏水。
所述复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为50℃的蒸馏水中，依次加入丁二酸二己酯磺酸钠、吐温-60，搅拌10min；
步骤2，将吡咯烷酮基羧酸钠加入步骤1得到的混合物中，补充蒸馏水，搅拌10min后制得复配型分散剂；所述复配型分散剂中，丁二酸二己酯磺酸钠的质量分数6％，吐温-60的质量分数为5％，吡咯烷酮基羧酸钠的质量分数为4％，余量为蒸馏水。
实施例五：
所述复配型分散剂由十二烷基二甲醚二磺酸钠、吐温-40、烷基醇酰胺和蒸馏水组成；所述复配型分散剂中，十二烷基二甲醚二磺酸钠的质量分数为1％，吐温-40的质量分数为1％，烷基醇酰胺的质量分数为1％，余量为蒸馏水。
所述复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为40℃的蒸馏水中，依次加入十二烷基二甲醚二磺酸钠、吐温-40，搅拌5min；
步骤2，将烷基醇酰胺加入步骤1得到的混合物中，补充蒸馏水，搅拌5min后制得复配型分散剂；所述复配型分散剂中，十二烷基二甲醚二磺酸钠的质量分数为1％，吐温-40的质量分数为1％，烷基醇酰胺的质量分数为1％，余量为蒸馏水。
实施例六：
所述复配型分散剂由脂肪醇聚氧乙烯醚(3)磺基琥珀酸单酯二钠、吐温-20、与硅酸二乙醇酰胺和蒸馏水组成；所述复配型分散剂中，脂肪醇聚氧乙烯醚(3)磺基琥珀酸单酯二钠的质量分数为10％，吐温-20的质量分数为10％，硅酸二乙醇酰胺的质量分数为10％，余量为蒸馏水。
所述复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为60℃的蒸馏水中，依次加入脂肪醇聚氧乙烯醚(3) 磺基琥珀酸单酯二钠、吐温-20，搅拌15min；
步骤2，将硅酸二乙醇酰胺加入步骤1得到的混合物中，搅拌15min后制得复配型分散剂；所述复配型分散剂中，脂肪醇聚氧乙烯醚(3)磺基琥珀酸单酯二钠的质量分数为10％，吐温-20的质量分数为10％，硅酸二乙醇酰胺的质量分数为10％，余量为蒸馏水。
实施例七：
所述复配型分散剂由丁二酸二己酯磺酸钠、十二烷基二甲醚二磺酸钠、吐温-20、吐温-60、聚乙烯吡咯烷酮、吡咯烷酮基羧酸钠和蒸馏水组成；所述复配型分散剂中，丁二酸二己酯磺酸钠的质量分数为4％，十二烷基二甲醚二磺酸钠的质量分数为3％，吐温-20的质量分数为3％，吐温-60的质量分数为3％，聚乙烯吡咯烷酮的质量分数为2％，吡咯烷酮基羧酸钠的质量分数为2％，余量为蒸馏水。
所述复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为45℃的蒸馏水中，依次加入阴离子型表面活性剂(丁二酸二己酯磺酸钠和十二烷基二甲醚二磺酸钠)、非离子型表面活性剂(吐温-20和吐温-60)，搅拌10min；
步骤2，将润湿剂(聚乙烯吡咯烷酮和吡咯烷酮基羧酸钠)加入步骤1得到的混合物中，补充蒸馏水，搅拌10min后制得复配型分散剂；所述复配型分散剂中，丁二酸二己酯磺酸钠的质量分数为4％，十二烷基二甲醚二磺酸钠的质量分数为3％，吐温-20的质量分数为3％，吐温-60的质量分数为3％，聚乙烯吡咯烷酮的质量分数为2％，吡咯烷酮基羧酸钠的质量分数为2％，余量为蒸馏水。
实施例八：
所述复配型分散剂由丁二酸二己酯磺酸钠、月桂基磺化琥珀酸单酯二钠、月桂醇琥珀酸单酯磺酸钠、吐温-20、吐温-80、吐温-60、聚乙烯吡咯烷酮、聚氧乙烯烷基酰胺、烷基酰胺和蒸馏水组成；所述复配型分散剂中，丁二酸二己酯磺酸钠的质量分数为2％，月桂基磺化琥珀酸单酯二钠的质量分数为1％，月桂醇琥珀酸单酯磺酸钠的质量分数为2％，吐温-20的质量分数为2％，吐温-80的质量分数为2％，吐温-60的质量分数为1％，聚乙烯吡 咯烷酮的质量分数为2％，聚氧乙烯烷基酰胺的质量分数为2％，烷基酰胺的质量分数为2％，余量为蒸馏水。
所述复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为55℃的蒸馏水中，依次加入阴离子型表面活性剂(丁二酸二己酯磺酸钠、月桂基磺化琥珀酸单酯二钠和月桂醇琥珀酸单酯磺酸钠)、非离子型表面活性剂(吐温-20、吐温-80和吐温-60)，搅拌15min；
步骤2，将润湿剂(聚乙烯吡咯烷酮、聚氧乙烯烷基酰胺和烷基酰胺)加入步骤1得到的混合物中，补充蒸馏水，搅拌15min，后制得复配型分散剂；所述复配型分散剂中，丁二酸二己酯磺酸钠的质量分数为2％，月桂基磺化琥珀酸单酯二钠的质量分数为1％，月桂醇琥珀酸单酯磺酸钠的质量分数为2％，吐温-20的质量分数为2％，吐温-80的质量分数为2％，吐温-60的质量分数为1％，聚乙烯吡咯烷酮的质量分数为2％，聚氧乙烯烷基酰胺的质量分数为2％，烷基酰胺的质量分数为2％，余量为蒸馏水。
以下为本发明混合电镀液的一种实施方式。
本发明混合电镀液，其包括所述复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子。
优选的，所述银基础水溶液中，KCN的质量体积浓度为90.0-200.0g/L。进一步的，所述银基础水溶液中，KCN的质量体积浓度为90.0g/L、100.0g/L、110.0g/L、120.0g/L、130.0g/L、140.0g/L、150.0g/L、160.0g/L、170.0g/L、180.0g/L、190.0g/L或200.0g/L。
优选的，所述银基础水溶液中，银离子的质量体积浓度为15.0-50.0g/L。进一步的，所述银基础水溶液中，银离子的质量体积浓度为15.0g/L、20.0g/L、25.0g/L、30.0g/L、35.0g/L、40.0g/L、45.0g/L或50.0g/L。
优选的，所述银离子由银板电解制得的水溶液提供。
优选的，所述混合电镀液中，石墨烯的质量体积浓度为1.0-20.0g/L。进一步的，所述混合电镀液中，石墨烯的质量体积浓度为1.0g/L、1.5g/L、2.0g/L、2.5g/L、3.0g/L、4.0g/L、5.0g/L、6.0g/L、7.0g/L、8.0g/L、9.0g/L、10.0g/L、11.0g/L、12.0g/L、13.0g/L、14.0g/L、15.0g/L、16.0g/L、17.0g/L、18.0g/L、19.0g/L或20.0g/L。
优选的，所述混合电镀液中，复配型分散剂的体积比浓度为15-45ml/L。进一步的，所述混合电镀液中，复配型分散剂的体积比浓度为15ml/L、20ml/L、25ml/L、30ml/L、35ml/L、40ml/L或45ml/L。
优选的，所述混合电镀液的滚镀电流密度为0.5-0.7A/dm 2。进一步的，所述混合电镀液的滚犊电流密度为0.5A/dm 2、0.6A/dm 2或0.7A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为0.7-1.0A/dm 2。进一步的，所述混合电镀液的挂镀电流密度为0.7A/dm 2、0.8A/dm 2、0.9A/dm 2或1.0A/dm 2。
以下为本发明混合电镀液制备方法的一种实施方式。
步骤1，制备银基础水溶液；所述银基础水溶液中，KCN的质量体积浓度为90-200g/L，银离子的质量体积浓度为15-50g/L。
步骤2，将所述的复配型分散剂和石墨烯依次加入银基础水溶液中，搅拌混合制得混合电镀液；所述混合电镀液中，复配型分散剂的体积比浓度为15-45ml/L，石墨烯的质量体积浓度为1.0-20g/L。
实施例九：
所述混合电镀液包括实施例一的复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，复配型分散剂的体积比浓度为30.0ml/L，石墨烯的质量体积浓度为2.0g/L；所述银基础水溶液中，KCN的质量体积浓度为150.0g/L，银离子的质量体积浓度为30.0g/L。
优选的，所述混合电镀液的滚镀电流密度为0.6A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为0.8A/dm 2。
实施例十：
所述混合电镀液包括实施例二的复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，复配型分散剂的体积比浓度为30.0ml/L，石墨烯的质量体积浓度为2.0g/L；所述银基础水溶液中，KCN的质量体积浓度为150.0g/L，银离子的质量体积浓度为30.0g/L。
优选的，所述混合电镀液的滚镀电流密度为0.6A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为0.8A/dm 2。
实施例十一：
所述混合电镀液包括实施例三的复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，复配型分散剂的体积比浓度为30.0ml/L，石墨烯的质量体积浓度为2.0g/L；所述银基础水溶液中，KCN的质量体积浓度为150.0g/L，银离子的质量体积浓度为30.0g/L。
优选的，所述混合电镀液的滚镀电流密度为0.6A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为0.8A/dm 2。
实施例十二：
所述混合电镀液包括实施例四的复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，复配型分散剂的体积比浓度为30.0ml/L，石墨烯的质量体积浓度为3.0g/L；所述银基础水溶液中，KCN的质量体积浓度为150.0g/L，银离子的质量体积浓度为30.0g/L。
优选的，所述混合电镀液的滚镀电流密度为0.6A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为0.8A/dm 2。
实施例十三：
所述混合电镀液包括实施例五的复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，复配型分散剂的体积比浓度为15.0ml/L，石墨烯的质量体积浓度为1.0g/L；所述银基础水溶液中，KCN的质量体积浓度为90.0g/L，银离子的质量体积浓度为15.0g/L。
优选的，所述混合电镀液的滚镀电流密度为0.7A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为1.0A/dm 2。
实施例十四：
所述混合电镀液包括实施例六的复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，复配型分散剂的体积比浓度为45.0ml/L，石墨烯的质量体积浓度为20.0.0g/L；所述银 基础水溶液中，KCN的质量体积浓度为200.0g/L，银离子的质量体积浓度为50.0g/L。
优选的，所述混合电镀液的滚镀电流密度为0.5A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为0.7A/dm 2。
实施例十五：
所述混合电镀液包括实施例七的复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，复配型分散剂的体积比浓度为35.0ml/L，石墨烯的质量体积浓度为10.0g/L；所述银基础水溶液中，KCN的质量体积浓度为180.0g/L，银离子的质量体积浓度为40g/L。
优选的，所述混合电镀液的滚镀电流密度为0.6A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为0.9A/dm 2。
实施例十六：
所述混合电镀液包括实施例八的复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，复配型分散剂的体积比浓度为25.0ml/L，石墨烯的质量体积浓度为5.0g/L；所述银基础水溶液中，KCN的质量体积浓度为130.0g/L，银离子的质量体积浓度为25.0g/L。
优选的，所述混合电镀液的滚镀电流密度为0.7A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为0.8A/dm 2。
实施例十七：
所述复配型分散剂由磺基丁二酸二辛基钠盐、吐温-40、吐温-60、聚乙烯吡咯烷酮和蒸馏水组成；所述复配型分散剂中，磺基丁二酸二辛基钠盐的质量分数为8％，吐温-40的质量分数为3％，吐温-60的质量分数为4％，聚乙烯吡咯烷酮的质量分数为5％，余量为蒸馏水。
所述复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为50℃的蒸馏水中，依次加入阴离子型表面活性剂(磺基丁二酸二辛基钠盐)、非离子型表面活性剂(吐温-40和吐温-60)，搅拌13min；
步骤2，将润湿剂(聚乙烯吡咯烷酮)加入步骤1得到的混合物中，补充蒸馏水，搅拌10min，后制得复配型分散剂；所述复配型分散剂中，磺基丁二酸二辛基钠盐的质量分数为8％，吐温-40的质量分数为3％，吐温-60的质量分数为4％，聚乙烯吡咯烷酮的质量分数为5％，余量为蒸馏水。
实施例十八：
所述复配型分散剂由磺基丁二酸二辛基钠盐、丁二酸二己酯磺酸钠，吐温-20、聚乙烯吡咯烷酮、月桂酸二乙醇酰胺和蒸馏水组成；所述复配型分散剂中，磺基丁二酸二辛基钠盐的质量分数为2％，丁二酸二己酯磺酸钠1％，吐温-20的质量分数为3％，聚乙烯吡咯烷酮的质量分数为1％，月桂酸二乙醇酰胺1％，余量为蒸馏水。
所述复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为60℃的蒸馏水中，依次加入阴离子型表面活性剂(磺基丁二酸二辛基钠盐和丁二酸二己酯磺酸钠)、非离子型表面活性剂(吐温-20)，搅拌15min；
步骤2，将润湿剂(聚乙烯吡咯烷酮和月桂酸二乙醇酰胺)加入步骤1得到的混合物中，补充蒸馏水，搅拌12min，后制得复配型分散剂；所述复配型分散剂中，磺基丁二酸二辛基钠盐的质量分数为2％，丁二酸二己酯磺酸钠1％，吐温-20的质量分数为3％，聚乙烯吡咯烷酮的质量分数为1％，月桂酸二乙醇酰胺1％，余量为蒸馏水。
实施例十九：
所述复配型分散剂由磺基丁二酸二辛基钠盐、月桂基磺化琥珀酸单酯二钠、十二烷基二甲醚二磺酸钠和二辛基磺化琥珀酸钠，吐温-20、吐温-60、吐温-80，聚乙烯吡咯烷酮、月桂酸二乙醇酰胺吡咯烷酮基羧酸钠，和蒸馏水组成；所述复配型分散剂中，磺基丁二酸二辛基钠盐的质量分数为2％，月桂基磺化琥珀酸单酯二钠的质量分数为2％，十二烷基二甲醚二磺酸钠的质量分数为3％，二辛基磺化琥珀酸钠的质量分数为2％，吐温-20的质量分数为2％，吐温-60的质量分数为5％，吐温-80的质量分数为2％，聚乙烯吡咯烷酮的质量分数为2％，月桂酸二乙醇酰胺的质量分数为3％，吡咯烷酮基羧酸钠的质量分数为2％，余量为蒸馏水。
所述复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为55℃的蒸馏水中，依次加入阴离子型表面活性剂(磺基丁二酸二辛基钠盐、月桂基磺化琥珀酸单酯二钠、十二烷基二甲醚二磺酸钠和二辛基磺化琥珀酸钠)、非离子型表面活性剂(吐温-20、吐温-60和吐温-80)，搅拌15min；
步骤2，将润湿剂(聚乙烯吡咯烷酮、月桂酸二乙醇酰胺和吡咯烷酮基羧酸钠)加入步骤1得到的混合物中，补充蒸馏水，搅拌15min，后制得复配型分散剂；所述复配型分散剂中，磺基丁二酸二辛基钠盐的质量分数为2％，月桂基磺化琥珀酸单酯二钠的质量分数为2％，十二烷基二甲醚二磺酸钠的质量分数为3％，二辛基磺化琥珀酸钠的质量分数为2％，吐温-20的质量分数为2％，吐温-60的质量分数为5％，吐温-80的质量分数为2％，聚乙烯吡咯烷酮的质量分数为2％，月桂酸二乙醇酰胺3％，吡咯烷酮基羧酸钠2％，余量为蒸馏水。
实施例二十：
所述复配型分散剂由二辛基磺化琥珀酸钠，吐温-40、吐温-60，烷基醇酰胺，以及蒸馏水组成；所述复配型分散剂中，二辛基磺化琥珀酸钠的质量分数为5％，吐温-40的质量分数为2％，吐温-60的质量分数为3％，烷基醇酰胺的质量分数为5％，余量为蒸馏水。
所述复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为50℃的蒸馏水中，依次加入阴离子型表面活性剂(二辛基磺化琥珀酸钠)、非离子型表面活性剂(吐温-40和吐温-60)，搅拌12min；
步骤2，将润湿剂(烷基醇酰胺)加入步骤1得到的混合物中，补充蒸馏水，搅拌12min，后制得复配型分散剂；所述复配型分散剂中，二辛基磺化琥珀酸钠的质量分数为5％，吐温-40的质量分数为2％，吐温-60的质量分数为3％，烷基醇酰胺的质量分数为2％，余量为蒸馏水。
实施例二十一：
所述复配型分散剂由二辛基磺化琥珀酸钠和磺基丁二酸二辛基钠盐，吐温-20和吐温-40，聚氧乙烯烷基酰胺和月桂酸二乙醇酰胺，以及蒸馏水组成；所述复配型分散剂中，二辛基磺化琥珀酸钠的质量分数为5％，磺基 丁二酸二辛基钠盐的质量分数为5％，吐温-20的质量分数为5％，吐温-40的质量分数为5％，聚氧乙烯烷基酰胺的质量分数为6％，月桂酸二乙醇酰胺的质量分数为4％，余量为蒸馏水。
所述复配型分散剂制备方法包括以下操作步骤：
步骤1，向温度为60℃的蒸馏水中，依次加入阴离子型表面活性剂(二辛基磺化琥珀酸钠)、非离子型表面活性剂(吐温-40和吐温-60)，搅拌12min；
步骤2，将润湿剂(烷基醇酰胺)加入步骤1得到的混合物中，补充蒸馏水，搅拌12min，后制得复配型分散剂；所述复配型分散剂中，二辛基磺化琥珀酸钠的质量分数为5％，吐温-40的质量分数为2％，吐温-60的质量分数为3％，烷基醇酰胺的质量分数为2％，余量为蒸馏水。
实施例二十二：
所述混合电镀液包括实施例十七的复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，复配型分散剂的体积比浓度为30.0ml/L，石墨烯的质量体积浓度为6.0g/L；所述银基础水溶液中，KCN的质量体积浓度为140.0g/L，银离子的质量体积浓度为35.0g/L。
优选的，所述混合电镀液的滚镀电流密度为0.7A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为0.8A/dm 2。
实施例二十三：
所述混合电镀液包括实施例十八的复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，复配型分散剂的体积比浓度为40.0ml/L，石墨烯的质量体积浓度为4.0g/L；所述银基础水溶液中，KCN的质量体积浓度为100.0g/L，银离子的质量体积浓度为20.0g/L。
优选的，所述混合电镀液的滚镀电流密度为0.7A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为1.0A/dm 2。
实施例二十四：
所述混合电镀液包括实施例十九的复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，复配型分散 剂的体积比浓度为25.0ml/L，石墨烯的质量体积浓度为9.0g/L；所述银基础水溶液中，KCN的质量体积浓度为160.0g/L，银离子的质量体积浓度为45.0g/L。
优选的，所述混合电镀液的滚镀电流密度为0.6A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为0.7A/dm 2。
实施例二十五：
所述混合电镀液包括实施例二十的复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，复配型分散剂的体积比浓度为33.0ml/L，石墨烯的质量体积浓度为7.0g/L；所述银基础水溶液中，KCN的质量体积浓度为140.0g/L，银离子的质量体积浓度为40.0g/L。
优选的，所述混合电镀液的滚镀电流密度为0.6A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为0.8A/dm 2。
实施例二十六：
所述混合电镀液包括实施例十九的复配型分散剂、银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，复配型分散剂的体积比浓度为17.0ml/L，石墨烯的质量体积浓度为10.0g/L；所述银基础水溶液中，KCN的质量体积浓度为190.0g/L，银离子的质量体积浓度为47.0g/L。
优选的，所述混合电镀液的滚镀电流密度为0.5A/dm 2。
优选的，所述混合电镀液的挂镀电流密度为0.7A/dm 2。
空白电镀液：
所述空白电镀液包括银基础水溶液和石墨烯，银基础水溶液包括KCN和银离子；所述混合电镀液中，石墨烯的质量体积浓度为2.0g/L；所述银基础水溶液中，KCN的质量体积浓度为150.0g/L，银离子的质量体积浓度为30.0g/L。
优选的，所述空白电镀液的滚镀电流密度为0.6A/dm 2。
优选的，所述空白电镀液的挂镀电流密度为0.8A/dm 2。
本发明混合电镀液，为一种石墨烯-银混合电镀液，通过以下操作对待 电镀产品进行电镀，以在待电镀产品上形成石墨烯-银混合镀层，具体的：对待电镀产品进行清洗，将清洗后的待电镀产品放入氰化钾溶液进行氰活化，对活化后的待电镀产品进行预镀银，将预镀银后的待电镀产品放入混合电镀液中进行电镀，电镀完成后，对电镀产品进行多次水洗。
表一以下为各实施例的混合电镀液、空白电镀液(未添加本发明复配型分散剂)的物理参数以及二者的电镀产品的实验数据(zeta电位数值的绝对值越大说明混合电镀液中石墨烯颗粒分散性越好、粒度检测片径数值越小说明混合电镀液中石墨烯分散性越好、耐磨性能数值越大说明电镀产品的耐磨性越好)：
表一：
Figure PCTCN2022084617-appb-000001
注：耐磨性能为平均每微米可承受次数，单位为/次。
通过以上实验数据表明，本发明混合电镀液，保证了石墨烯在混合电镀液中稳定均匀分布，能显著提高银-石墨烯镀层中石墨烯分布的均匀程度，从而显著提高电镀产品的产品性能(包括导电性、导热性、耐磨性等)。
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简 单推演或替换，都应当视为属于本发明的保护范围。

Claims (13)

  1. 一种复配型分散剂，其特征在于，其由蒸馏水、非离子型表面活性剂、阴离子型表面活性剂和润湿剂组成；所述非离子型表面活性剂为吐温类化合物，阴离子型表面活性剂为烃基磺酸盐类化合物，润湿剂为酰胺类化合物。
  2. 根据权利要求1所述的复配型分散剂，其特征在于：所述润湿剂包括聚乙烯吡咯烷酮、烷基酰胺、月桂酸二乙醇酰胺、吡咯烷酮基羧酸钠、聚氧乙烯烷基酰胺和烷基醇酰胺中的一种或多种。
  3. 根据权利要求1所述的复配型分散剂，其特征在于：所述非离子型表面活性剂包括吐温-20、吐温-40、吐温-60和吐温-80中的一种或多种。
  4. 根据权利要求1所述的复配型分散剂，其特征在于：所述阴离子型表面活性剂包括丁二酸二己酯磺酸钠、月桂醇琥珀酸单酯磺酸钠、十二烷基二苯醚二磺酸钠、月桂基磺化琥珀酸单酯二钠、脂肪醇聚氧乙烯醚(3)磺基琥珀酸单酯二钠、磺基丁二酸二辛基钠盐和二辛基磺化琥珀酸钠中的一种或多种。
  5. 根据权利要求1所述的复配型分散剂，其特征在于：所述复配型分散剂中，非离子型表面活性剂的质量分数为1-10％；
    所述复配型分散剂中，润湿剂的质量分数为1-10％；
    所述复配型分散剂中，阴离子型表面活性剂的质量分数为1-10％。
  6. 一种复配型分散剂制备方法，其特征在于，其包括以下步骤：
    步骤1，向温度为T0的蒸馏水中，加入阴离子型表面活性剂和非离子型表面活性剂，搅拌时间t0，40℃≤T0≤60℃，5≤t0≤15min；
    步骤2，将润湿剂加入步骤1所得混合物中，补充蒸馏水，搅拌时间t1，得到复配型分散剂，5min≤t1≤15min；所述复配型分散剂中，非离子型表面活性剂的质量分数为1-10％，阴离子型表面活性剂的质量分数为1-10％，润湿剂的质量分数为1-10％，余量为蒸馏水。
  7. 根据权利要求6所述的复配型分散剂制备方法，其特征在于：所述润湿剂包括聚乙烯吡咯烷酮、烷基酰胺、月桂酸二乙醇酰胺、吡咯烷酮基羧酸钠、聚氧乙烯烷基酰胺和烷基醇酰胺中的一种或多种。
  8. 根据权利要求6所述的复配型分散剂制备方法，其特征在于：所述 非离子型表面活性剂包括吐温-20、吐温-40、吐温-60和吐温-80中的一种或多种。
  9. 根据权利要求6所述的复配型分散剂制备方法，其特征在于：所述阴离子型表面活性剂包括丁二酸二己酯磺酸钠、月桂醇琥珀酸单酯磺酸钠、十二烷基二苯醚二磺酸钠、月桂基磺化琥珀酸单酯二钠、脂肪醇聚氧乙烯醚(3)磺基琥珀酸单酯二钠、磺基丁二酸二辛基钠盐和二辛基磺化琥珀酸钠中的一种或多种。
  10. 一种混合电镀液，其特征在于，包括权利要求1-5任意一项所述的复配型分散剂、银基础水溶液和石墨烯，银基水溶础液包括KCN和银离子。
  11. 根据权利要求10所述的混合电镀液，其特征在于：
    所述混合电镀液中，复配型分散剂的体积比浓度为15.0-45.0ml/L；
    所述银基础水溶液中，KCN的质量体积浓度为90.0-200.0g/L；
    所述银基础水溶液中，银离子的质量体积浓度为15.0-50.0g/L；
    所述混合电镀液中，石墨烯的质量体积浓度为1.0-20.0g/L。
  12. 根据权利要求10所述的混合电镀液，其特征在于：所述混合电镀液的滚镀电流密度为0.5-0.7A/dm 3；
    所述混合电镀液的挂镀电流密度为0.7-1.0A/dm 3。
  13. 一种混合电镀液制备方法，其特征在于，其包括以下步骤：
    步骤1，制备银基础水溶液；所述银基础水溶液中，KCN的质量体积浓度为90.0-200.0g/L，银离子的质量体积浓度为15.0-50.0g/L；
    步骤2，将权利要求1-5任意一项所述的复配型分散剂和石墨烯依次加入银基础水溶液中，搅拌混合制得混合电镀液；所述混合电镀液中，复配型分散剂的体积比浓度为15.0-45.0ml/L，石墨烯的质量体积浓度为1.0-20.0g/L。
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