WO2022206927A1 - 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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WO2022206927A1
WO2022206927A1 PCT/CN2022/084645 CN2022084645W WO2022206927A1 WO 2022206927 A1 WO2022206927 A1 WO 2022206927A1 CN 2022084645 W CN2022084645 W CN 2022084645W WO 2022206927 A1 WO2022206927 A1 WO 2022206927A1
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WIPO (PCT)
Prior art keywords
compound
dispersant
electroplating solution
silver
graphene
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PCT/CN2022/084645
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English (en)
French (fr)
Inventor
吉燊
徐正利
周津裕
曾浪
申奇
林隽裕
郑建勇
胡益明
王川
林荣臻
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浙江正泰电器股份有限公司
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Application filed by 浙江正泰电器股份有限公司 filed Critical 浙江正泰电器股份有限公司
Priority to EP22779107.6A priority Critical patent/EP4242360A1/en
Priority to US18/252,845 priority patent/US20240003035A1/en
Priority to JP2023550121A priority patent/JP2024517050A/ja
Publication of WO2022206927A1 publication Critical patent/WO2022206927A1/zh

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    • 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 effectively block or slow down the agglomeration of graphene in the dispersion; and also provides a compound dispersant preparation method, which operates Simple, the prepared compound dispersant can effectively block or slow down the agglomeration of graphene in the dispersion; also provides a mixed electroplating solution in which graphene is dispersed uniformly and stably; and a preparation method of the mixed electroplating solution is also provided.
  • the operation is simple, and in the prepared mixed electroplating solution, the graphene is dispersed uniformly and stably.
  • a compound dispersant which is composed of distilled water, a non-ionic surfactant and a wetting agent; the non-ionic surfactant is a Tween compound, and the wetting agent includes a hydrocarbyl sulfate salt compound and a hydrocarbyl sulfonic acid acid compound.
  • the hydrocarbyl sulfate compound includes 2-ethylhexyl sulfate sodium salt.
  • the mass fraction of the hydrocarbyl sulfate compound is 5-8%.
  • the hydrocarbyl sulfonate compound includes at least one of sodium dioctyl sulfosuccinate and sodium dihexyl succinate.
  • the mass fraction of the hydrocarbyl sulfonate compound is 6-10%.
  • the Tween compound includes Tween-20.
  • the mass fraction of the Tween compound is 4-6%.
  • a method for preparing a compound dispersant comprising the following steps:
  • Step 1 add hydrocarbyl sulfate compound and Tween compound into distilled water with temperature T0, 40°C ⁇ T0 ⁇ 60°C, and stir for time t0, 5min ⁇ t0 ⁇ 10min;
  • Step 2 adding the hydrocarbyl sulfonate compound to the mixture obtained in step 1, supplementing distilled water, and stirring for a time t1, 5min ⁇ t1 ⁇ 15min, to prepare a compound dispersant.
  • a mixed electroplating solution includes the compound dispersant, a silver basic aqueous solution and graphene; 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 silver ions is 15.0-50.0 g/L.
  • the volume ratio concentration of the compound dispersant is 15.0-50.0ml/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 2 .
  • the rack plating current density of the mixed electroplating solution is 0.7-1.0 A/dm 2 .
  • a method for preparing a mixed electroplating solution comprising the following steps:
  • Step S1 preparing 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 S2 adding the described composite dispersant and graphene to the silver basic aqueous solution and stirring;
  • step S3 in the mixing obtained in step S2, the silver basic aqueous solution is supplemented and stirred to prepare a mixed electroplating solution;
  • the mass volume concentration is 1.0-20.0g/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 present invention has simple operation, and the prepared compound dispersant can effectively block or slow down the agglomeration of graphene in the dispersion, and ensure that the graphene is uniformly and stably dispersed in the dispersion.
  • the compound dispersant can effectively block or slow down the agglomeration of graphene, ensure uniform and stable dispersion of graphene in the mixed electroplating solution, thereby improving the graphene-silver mixed coating of electroplating products.
  • the uniformity of alkene dispersion improves the product performance of electroplating products.
  • the compound dispersant of the present invention is composed of distilled water, a non-ionic surfactant and a wetting agent; the non-ionic surfactant is a Tween compound, and the wetting agent includes a hydrocarbyl sulfate ester salt compound and a hydrocarbyl sulfonic acid acid 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 preparation method of the compound dispersant of the present invention comprises the following steps:
  • Step 1 add hydrocarbyl sulfate compound and Tween compound into distilled water with temperature T0, 40°C ⁇ T0 ⁇ 60°C, and stir for time t0, 5min ⁇ t0 ⁇ 10min;
  • Step 2 adding the hydrocarbyl sulfonate compound to the mixture obtained in step 1, supplementing distilled water and stirring for a time t1, 5min ⁇ t1 ⁇ 15min, to prepare a compound dispersant.
  • the preparation method of the compound dispersant of the present invention has simple operation, and the prepared compound dispersant can effectively block or slow down the agglomeration of graphene in the dispersion, and ensure that the graphene is uniformly and stably dispersed in the dispersion.
  • the mixed electroplating solution of the present invention includes the compound dispersant, a silver basic aqueous solution and graphene; the silver basic aqueous solution includes KCN and silver ions.
  • the compound dispersant can effectively block or slow down the agglomeration of graphene, ensure uniform and stable dispersion of graphene in the mixed electroplating solution, thereby improving the graphene-silver mixed coating of electroplating products.
  • the uniformity of alkene dispersion improves the product performance of electroplating products.
  • the preparation method of the mixed electroplating solution of the present invention comprises the following steps:
  • Step S1 preparing 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 S2 adding the described composite dispersant and graphene to the silver basic aqueous solution and stirring;
  • step S3 in the mixing obtained in step S2, the silver basic aqueous solution is supplemented and stirred to prepare a mixed electroplating solution;
  • the mass volume concentration is 1.0-20.0g/L.
  • the method for preparing the mixed electroplating solution of the present invention is simple in operation, and in the prepared mixed electroplating solution, graphene is dispersed evenly and stably.
  • the compound dispersant of the present invention is composed of distilled water, a non-ionic surfactant and a wetting agent; the non-ionic surfactant is a Tween compound, and the wetting agent includes a hydrocarbyl sulfate ester salt compound and a hydrocarbyl sulfonic acid acid compound.
  • the hydrocarbyl sulfate compound includes 2-ethylhexyl sulfate sodium salt.
  • the mass fraction of the hydrocarbyl sulfate salt compound is 5-8%. Further, in the compound dispersant of the present invention, the mass fraction of the hydrocarbyl sulfate salt compound is 5%, 6%, 7% or 8%.
  • the hydrocarbyl sulfonate compound includes at least one of sodium dioctyl sulfosuccinate and sodium dihexyl succinate.
  • the mass fraction of the hydrocarbyl sulfonate compound is 6-10%. Further, in the compound dispersant of the present invention, the mass fraction of the hydrocarbyl sulfonate compound is 6%, 7%, 8%, 9% or 10%.
  • the Tween compound includes Tween-20.
  • the Tween compound can also be one or more of Tween-20, Tween-40, Tween-60, and Tween-80; wherein, Tween-20 has the best effect, Therefore, in the compound dispersant of the present invention, the Tween compound is preferably Tween-20.
  • the mass fraction of the Tween compound is 4-6%. Further, in the compound dispersant of the present invention, the mass fraction of the Tween compound is 4%, 5% or 5%.
  • the preparation method of the compound dispersant of the present invention comprises the following steps:
  • Step 1 add hydrocarbyl sulfate compound and Tween compound into distilled water with temperature T0, 40°C ⁇ T0 ⁇ 60°C, and stir for time t0, 5min ⁇ t0 ⁇ 10min.
  • T0 is 40°C, 45°C, 50°C, 55°C or 60°C.
  • t0 is 5min, 6min, 7min, 8min, 9min or 10min.
  • Step 2 adding the hydrocarbyl sulfonate compound to the mixture obtained in step 1, supplementing distilled water and stirring for a time t1, 5min ⁇ t1 ⁇ 15min, to prepare a compound dispersant.
  • t1 is 5min, 6min, 7min, 8min, 9min or 10min.
  • pre-prepared M kg compound dispersant calculate the required distilled water quality; Step 1, take 15-45% (15%, 20%, 25%, 30%, 35%, 40% of the required distilled water quality) or 45%) heated to temperature T0, add hydrocarbyl sulfate compound and Tween compound, and stir for time t0; step 2, add hydrocarbyl sulfonate compound to the mixture obtained in step 1, add distilled water and stir for time t1, prepare To obtain compound dispersant M kg.
  • the compound dispersant in this embodiment is composed of distilled water, a nonionic surfactant and a wetting agent;
  • the nonionic surfactant includes a hydrocarbyl sulfate compound and a hydrocarbyl sulfonate compound, and the hydrocarbyl sulfate compound includes 2-ethylhexyl sulfate sodium salt, the hydrocarbon sulfonate compound includes sodium dioctyl sulfosuccinate;
  • the nonionic surfactant is a Tween compound, and the Tween compound includes Tween-20;
  • the mass fraction of the hydrocarbyl sulfate compound is 5%
  • the mass fraction of the hydrocarbyl sulfonate compound is 6%
  • the mass fraction of the Tween compound is 4%
  • the balance is distilled water.
  • Step 1 add the hydrocarbyl sulfate compound and the Tween compound into distilled water at a temperature of 50°C, and stir for 10 min.
  • step 2 the hydrocarbyl sulfonate compound is added to the mixture obtained in step 1, distilled water is supplemented, and the mixture is stirred for 10 minutes to prepare a compound dispersant.
  • the compound dispersant in this embodiment is composed of distilled water, a nonionic surfactant and a wetting agent;
  • the nonionic surfactant includes a hydrocarbyl sulfate compound and a hydrocarbyl sulfonate compound, and the hydrocarbyl sulfate compound includes 2-ethylhexyl sulfate sodium salt, the hydrocarbon sulfonate compound includes sodium dioctyl sulfosuccinate;
  • the nonionic surfactant is a Tween compound, and the Tween compound includes Tween-20;
  • the mass fraction of the hydrocarbyl sulfate compound is 8%, the mass fraction of the hydrocarbyl sulfonate compound is 10%, the mass fraction of the Tween compound is 6%, and the balance is distilled water.
  • Step 1 add the hydrocarbyl sulfate compound and the Tween compound into distilled water at a temperature of 50°C, and stir for 10 min.
  • step 2 the hydrocarbyl sulfonate compound is added to the mixture obtained in step 1, distilled water is supplemented, and the mixture is stirred for 10 minutes to prepare a compound dispersant.
  • the compound dispersant in this embodiment is composed of distilled water, a nonionic surfactant and a wetting agent;
  • the nonionic surfactant includes a hydrocarbyl sulfate compound and a hydrocarbyl sulfonate compound, and the hydrocarbyl sulfate compound includes 2-ethylhexyl sulfate sodium salt, the hydrocarbon sulfonate compound includes sodium dioctyl sulfosuccinate;
  • the nonionic surfactant is a Tween compound, and the Tween compound includes Tween-20;
  • the mass fraction of the hydrocarbyl sulfate compound is 7%
  • the mass fraction of the hydrocarbyl sulfonate compound is 8%
  • the mass fraction of the Tween compound is 5%
  • the balance is distilled water.
  • Step 1 add the hydrocarbyl sulfate compound and the Tween compound into distilled water at a temperature of 60° C., and stir for 5 min.
  • step 2 the hydrocarbyl sulfonate compound is added to the mixture obtained in step 1, and distilled water is supplemented and stirred for 15 minutes to prepare a compound dispersant.
  • the mixed electroplating solution of the present invention includes the compound dispersant, a silver basic aqueous solution and graphene; 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 volume ratio concentration of the compound dispersant is 15.0-50.0 ml/L.
  • the volume ratio concentration of the compound dispersant is 15.0ml/L, 20.0ml/L, 25.0ml/L, 30.0ml/L, 35.0ml/L, 40.0ml/L, 45.0ml/L or 50.0ml/L.
  • the mass volume concentration of graphene is 1.0-20.0 g/L.
  • the mass volume concentration of graphene is 1.0g/L, 2.0g/L, 3.0g/L, 4.0g/L, 5.0g/L, 6.0g/L, 7.0g/L 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 barrel plating current density of the mixed electroplating solution of the present invention is 0.5-0.7 A/dm 2 .
  • the barrel plating current density of the mixed electroplating solution of the present invention is 0.5A/dm 2 , 0.6A/dm 2 or 0.7A/dm 2
  • the rack plating current density of the mixed electroplating solution of the present invention is 0.7-1.0 A/dm 3 . Further, the rack plating current density of the mixed electroplating solution of the present invention 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.
  • the preparation method of the mixed electroplating solution of the present invention comprises the following operation steps:
  • Step S1 preparing 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 S2 adding the composite dispersant and graphene described in any one of claims 1-7 to the silver base aqueous solution and stirring;
  • step S3 in the mixing obtained in step S2, the silver basic aqueous solution is supplemented and stirred to prepare a mixed electroplating solution;
  • the mass volume concentration is 1.0-20.0g/L.
  • the mixed electroplating solution in this embodiment includes the compound dispersant of Embodiment 1, a silver basic aqueous solution and graphene; the silver basic aqueous solution includes KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 150.0 g /L, the mass volume concentration of silver ions is 30.0g/L; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 30.0ml/L, and the mass volume concentration of graphene is 2.0g/L.
  • the barrel plating current density of the mixed electroplating solution in this embodiment is 0.6 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution in this embodiment is 0.8 A/dm 2 .
  • the mixed electroplating solution of this embodiment includes the compound dispersant of embodiment 2, a silver basic aqueous solution and graphene; the silver basic aqueous solution includes KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 150.0 g /L, the mass volume concentration of silver ions is 30.0g/L; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 30.0ml/L, and the mass volume concentration of graphene is 2.0g/L.
  • the barrel plating current density of the mixed electroplating solution in this embodiment is 0.6 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution in this embodiment is 0.8 A/dm 2 .
  • the mixed electroplating solution of this embodiment includes the compound dispersant of Embodiment 2, a silver basic aqueous solution and graphene; the silver basic aqueous solution includes KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 200.0 g /L, the mass volume concentration of silver ions is 50.0g/L; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 50.0ml/L, and the mass volume concentration of graphene is 20.0g/L.
  • the barrel plating current density of the mixed electroplating solution in this embodiment is 0.5 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution in this embodiment is 0.7 A/dm 2 .
  • the mixed electroplating solution of this embodiment includes the compound dispersant of Embodiment 1, a silver basic aqueous solution and graphene; the silver basic aqueous solution includes KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 90 g/g/ L, the mass volume concentration of silver ions is 15.0g/L; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 15.0ml/L, and the mass volume concentration of graphene is 1.0g/L.
  • the barrel plating current density of the mixed electroplating solution in this embodiment is 0.7 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution in this embodiment is 1.0A/dm 2 .
  • the mixed electroplating solution of this embodiment includes the compound dispersant of Embodiment 3, a silver basic aqueous solution and graphene; the silver basic aqueous solution includes KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 150 g/g L, the mass volume concentration of silver ions is 35.0g/L; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 35.0ml/L, and the mass volume concentration of graphene is 10.0g/L.
  • the barrel plating current density of the mixed electroplating solution in this embodiment is 0.6 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution in this embodiment is 0.9 A/dm 2 .
  • the blank electroplating solution includes a silver basic aqueous solution and graphene; the silver basic aqueous solution includes KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 150.0 g/L, and the mass volume concentration of silver ions is 30.0 g/L. g/L; in the mixed electroplating solution, the mass volume concentration of graphene is 2.0 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 compound dispersant in this embodiment is composed of distilled water, a nonionic surfactant and a wetting agent;
  • the nonionic surfactant includes a hydrocarbyl sulfate compound and a hydrocarbyl sulfonate compound, and the hydrocarbyl sulfate compound includes 2-ethylhexyl sulfate sodium salt, the hydrocarbyl sulfonate compound includes sodium dihexyl succinate sulfonate;
  • the nonionic surfactant is a Tween compound, and the Tween compound includes Tween-20;
  • the mass fraction of the hydrocarbyl sulfate compound is 6%
  • the mass fraction of the hydrocarbyl sulfonate compound is 9%
  • the mass fraction of the Tween compound is 5%
  • the balance is distilled water.
  • Step 1 add the hydrocarbyl sulfate compound and the Tween compound into distilled water with a temperature of 45°C, and stir for 8 min.
  • step 2 the hydrocarbyl sulfonate compound is added to the mixture obtained in step 1, and distilled water is supplemented and stirred for 12 minutes to prepare a compound dispersant.
  • the compound dispersant in this embodiment is composed of distilled water, a nonionic surfactant and a wetting agent;
  • the nonionic surfactant includes a hydrocarbyl sulfate compound and a hydrocarbyl sulfonate compound, and the hydrocarbyl sulfate compound includes 2-Ethylhexyl sulfate sodium salt, hydrocarbyl sulfonate compounds include dihexyl succinate sodium sulfonate and dioctyl sodium sulfosuccinate;
  • Warm compounds include Tween-20; in the compound dispersant, the mass fraction of the hydrocarbyl sulfate compound is 6%, and the mass fraction of the hydrocarbyl sulfonate compound is 8% (wherein the dioctyl sulfosuccinic acid is 8%).
  • the mass fraction of sodium is 3%, the mass fraction of sodium dihexyl succinate sulfonate is 5%), the
  • Step 1 add a hydrocarbyl sulfate compound and a Tween compound to distilled water at a temperature of 55° C., and stir for 9 min.
  • step 2 the hydrocarbyl sulfonate compound is added to the mixture obtained in step 1, distilled water is supplemented, and the mixture is stirred for 8 minutes to prepare a compound dispersant.
  • the mixed electroplating solution of this embodiment includes the compound dispersant of Example 9, a silver basic aqueous solution and graphene; the silver basic aqueous solution includes KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 170.0 g /L, the mass volume concentration of silver ions is 25.0g/L; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 20.0ml/L, and the mass volume concentration of graphene is 8.0g/L.
  • the barrel plating current density of the mixed electroplating solution in this embodiment is 0.6 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution in this embodiment is 0.8 A/dm 2 .
  • the mixed electroplating solution of this embodiment includes the compound dispersant of embodiment 10, a silver basic aqueous solution and graphene; the silver basic aqueous solution includes KCN and silver ions; in the silver basic aqueous solution, the mass volume concentration of KCN is 140.0 g /L, the mass volume concentration of silver ions is 35.0g/L; in the mixed electroplating solution, the volume ratio concentration of the compound dispersant is 40.0ml/L, and the mass volume concentration of graphene is 15.0g/L.
  • the barrel plating current density of the mixed electroplating solution in this embodiment is 0.7 A/dm 2 .
  • the rack plating current density of the mixed electroplating solution in this embodiment is 0.7 A/dm 2 .
  • the present embodiment also discloses an electroplating method, using the mixed electroplating solution to electroplate a graphene-silver mixed electroplating layer for a product to be electroplated, which specifically includes the following operations: cleaning the product to be electroplated, and placing the cleaned product to be electroplated into cyanide
  • the potassium chloride solution is activated by cyanide, the cyanide-activated product to be electroplated is pre-plated with silver, the pre-silvered product to be electroplated is put into the mixed electroplating solution for electroplating, and the electroplated product is washed with water for many 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) of each embodiment, and the experimental data (zeta potential value of the electroplating product of each embodiment and the electroplating product of the blank electroplating solution)
  • 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.), which increases the wear resistance of electroplating products by more than 5 times.

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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和润湿剂组成；所述非离子型表面活性剂为吐温类化合物，润湿剂包括烃基硫酸酯盐化合物和烃基磺酸盐化合物；所述复配型分散剂，其能有效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，其操作简单，制备的复配型分散剂能有效阻断或减缓分散液中石墨烯的团聚。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，其操作简单，制备的混合电镀液中，石墨烯分散均匀、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，其能有效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，其操作简单，制备的复配型分散剂能有效阻断或减缓分散液中石墨烯的团聚；还提供一种混合电镀液，其石墨烯分散均匀、稳定；还提供一种混合电镀液制备方法，其操作简单，制备的混合电镀液中，石墨烯分散均匀、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和润湿剂组成；所述非离子型表面活性剂为吐温类化合物，润湿剂包括烃基硫酸酯盐化合物和烃基磺酸盐化合物。
优选的，所述烃基硫酸酯盐化合物包括2-乙基己基硫酸酯钠盐。
优选的，所述复配型分散剂中，烃基硫酸酯盐化合物的质量分数为5-8％。
优选的，所述烃基磺酸盐化合物包括二辛基磺化琥珀酸钠和丁二酸二己酯磺酸钠中的至少一个。
优选的，所述复配型分散剂中，烃基磺酸盐化合物的质量分数为6-10％。
优选的，所述吐温类化合物包括吐温-20。
优选的，所述复配型分散剂中，吐温类化合物的质量分数为4-6％。
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，40℃≤T0≤60℃，加入烃基硫酸酯盐化合物和吐温类化合物，并搅拌时间t0，5min≤t0≤10min；
步骤2，将烃基磺酸盐化合物加入步骤1所得混合物中，补充蒸馏水，并搅拌时间t1，5min≤t1≤15min，制得复配型分散剂。
一种混合电镀液，其包括所述的复配型分散剂、银基础水溶液和石墨烯；所述银基础水溶液包括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。
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，复配型分散剂的体积比浓度为15.0-50.0ml/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 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。
一种混合电镀液制备方法，其包括以下步骤：
步骤S1，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S2，将所述的复配型分散剂、石墨烯加入银基础水溶液中并搅拌；
步骤S3，向步骤S2所得混合中，补充银基础水溶液并搅拌，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15.0-50.0ml/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，制备的复配型分散剂能有效阻断或减缓分散液中石墨烯的团聚，保证石墨烯均匀、稳定的分散在分散液中。
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，保证石墨烯在混合电镀液中均匀、稳定的分散，从而提高电镀产品的石墨烯-银混合镀层中石墨烯分散的均匀性，提高电镀产品的产品性能。
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、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、混合电镀液及制备方法不限于以下实施例的描述。
本发明复配型分散剂，其由蒸馏水、非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，润湿剂包括烃基硫酸酯盐化合物和烃基磺酸盐化合物。
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，40℃≤T0≤60℃，加入烃基硫酸酯盐化合物和吐温类化合，并搅拌时间t0，5min≤t0≤10min；
步骤2，将烃基磺酸盐化合物加入步骤1所得混合物中，补充蒸馏水并搅拌时间t1，5min≤t1≤15min，制得复配型分散剂。
本发明复配型分散剂制备方法，其操作简单，制备的复配型分散剂能有效阻断或减缓分散液中石墨烯的团聚，保证石墨烯均匀、稳定的分散在分散液中。
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；所述银基础水溶液包括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，保证石墨烯在混合电镀液中均匀、稳定的分散，从而提高电镀产品的石墨烯-银混合镀层中石墨烯分散的均匀性，提高电镀产品的产品性能。
本发明混合电镀液制备方法，其包括以下步骤：
步骤S1，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S2，将所述的复配型分散剂、石墨烯加入银基础水溶液中并搅拌；
步骤S3，向步骤S2所得混合中，补充银基础水溶液并搅拌，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15.0-50.0ml/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，其操作简单，制备的混合电镀液中，石墨烯分散均匀、稳定。
以下将结合具体实施例对本发明复配型分散剂及制备方法、混合电镀液及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，其由蒸馏水、非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，润湿剂包括烃基硫酸酯盐化合物和烃基磺酸盐化合物。
优选的，所述烃基硫酸酯盐化合物包括2-乙基己基硫酸酯钠盐。
优选的，本发明复配型分散剂中，烃基硫酸酯盐化合物的质量分数为5-8％。进一步的，本发明复配型分散剂中，烃基硫酸酯盐化合物的质量分数为5％、6％、7％或8％。
优选的，所述烃基磺酸盐化合物包括二辛基磺化琥珀酸钠和丁二酸二己酯磺酸钠中的至少一个。
优选的，本发明复配型分散剂中，烃基磺酸盐化合物的质量分数为6-10％。进一步的，本发明复配型分散剂中，烃基磺酸盐化合物的质量分数为6％、7％、8％、9％或10％。
优选的，所述吐温类化合物包括吐温-20。进一步的，所述吐温类化合物还可以是吐温-20、吐温-40、吐温-60、吐温-80中的一种或多种；其中，吐温-20的效果最佳，因此在本发明复配型分散剂中，吐温类化合物优选为吐温-20。
优选的，本发明复配型分散剂中，吐温类化合物的质量分数为4-6％。进一步的，本发明复配型分散剂中，吐温类化合物的质量分数为4％、5％或5％。
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，其包括以下步骤：
步骤1，向温度为T0的蒸馏水中，40℃≤T0≤60℃，加入烃基硫酸酯盐化合物和吐温类化合物，并搅拌时间t0，5min≤t0≤10min。
优选的，T0为40℃、45℃、50℃、55℃或60℃。
优选的，t0为5min、6min、7min、8min、9min或10min。
步骤2，将烃基磺酸盐化合物加入步骤1所得混合物中，补充蒸馏水并搅拌时间t1，5min≤t1≤15min，制得复配型分散剂。
优选的，t1为5min、6min、7min、8min、9min或10min。
具体的，预配制M kg复配型分散剂，计算所需蒸馏水质量；步骤1，取所需蒸馏水质量的15-45％(15％、20％、25％、30％、35％、40％或45％)加热至温度T0，加入烃基硫酸酯盐化合物和吐温类化合物，并搅拌时间t0；步骤2，将烃基磺酸盐化合物加入步骤1所得混合物中，补充蒸馏水并搅拌时间t1，制得复配型分散剂M kg。
以下为本发明复配型分散剂及制备方法的具体实施例。
实施例1：
本实施例复配型分散剂由蒸馏水、非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包括烃基硫酸酯盐化合物和烃基磺酸盐化合物，烃基硫酸酯盐化合物包括2-乙基己基硫酸酯钠盐，烃基磺酸盐化合物包括 二辛基磺化琥珀酸钠；所述非离子型表面活性剂为吐温类化合物，吐温类化合物包括吐温-20；所述复配型分散剂中，烃基硫酸酯盐化合物的质量分数为5％，烃基磺酸盐化合物的质量分数为6％，吐温类化合物的质量分数为4％，余量为蒸馏水。
本实施例复配型分散剂制备方法包括以下步骤：
步骤1，向温度为50℃的蒸馏水中，加入烃基硫酸酯盐化合物和吐温类化合物，搅拌10min。
步骤2，将烃基磺酸盐化合物加入步骤1所得混合物中，补充蒸馏水并搅拌10min，制得复配型分散剂。
实施例2：
本实施例复配型分散剂由蒸馏水、非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包括烃基硫酸酯盐化合物和烃基磺酸盐化合物，烃基硫酸酯盐化合物包括2-乙基己基硫酸酯钠盐，烃基磺酸盐化合物包括二辛基磺化琥珀酸钠；所述非离子型表面活性剂为吐温类化合物，吐温类化合物包括吐温-20；所述复配型分散剂中，烃基硫酸酯盐化合物的质量分数为8％，烃基磺酸盐化合物的质量分数为10％，吐温类化合物的质量分数为6％，余量为蒸馏水。
本实施例复配型分散剂制备方法包括以下步骤：
步骤1，向温度为50℃的蒸馏水中，加入烃基硫酸酯盐化合物和吐温类化合物，搅拌10min。
步骤2，将烃基磺酸盐化合物加入步骤1所得混合物中，补充蒸馏水并搅拌10min，制得复配型分散剂。
实施例3：
本实施例复配型分散剂由蒸馏水、非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包括烃基硫酸酯盐化合物和烃基磺酸盐化合物，烃基硫酸酯盐化合物包括2-乙基己基硫酸酯钠盐，烃基磺酸盐化合物包括二辛基磺化琥珀酸钠；所述非离子型表面活性剂为吐温类化合物，吐温类化合物包括吐温-20；所述复配型分散剂中，烃基硫酸酯盐化合物的质量分数为7％，烃基磺酸盐化合物的质量分数为8％，吐温类化合物的质量分数为 5％，余量为蒸馏水。
本实施例复配型分散剂制备方法包括以下步骤：
步骤1，向温度为60℃的蒸馏水中，加入烃基硫酸酯盐化合物和吐温类化合物，搅拌5min。
步骤2，将烃基磺酸盐化合物加入步骤1所得混合物中，补充蒸馏水并搅拌15min，制得复配型分散剂。
以下为本发明混合电镀液的一种实施方式。
本发明混合电镀液包括所述复配型分散剂、银基础水溶液和石墨烯；所述银基础水溶液包括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，本发明混合电镀液中，复配型分散剂的体积比浓度为15.0-50.0ml/L。进一步的，本发明混合电镀液中，复配型分散剂的体积比浓度为15.0ml/L、20.0ml/L、25.0ml/L、30.0ml/L、35.0ml/L、40.0ml/L、45.0ml/L或50.0ml/L。
优选的，本发明混合电镀液中，石墨烯的质量体积浓度为1.0-20.0g/L。进一步的，本发明混合电镀液中，石墨烯的质量体积浓度为1.0g/L、2.0g/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，本发明混合电镀液的滚镀电流密度为0.5-0.7A/dm 2。进一步的，本发明混合电镀液的滚镀电流密度为0.5A/dm 2、0.6A/dm 2或0.7A/dm 2
优选的，本发明混合电镀液的挂镀电流密度为0.7-1.0A/dm 3。进一步的，本发明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。
本发明混合电镀液制备方法，其包括以下操作步骤：
步骤S1，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S2，将权利要求1-7任意一项所述的复配型分散剂、石墨烯加入银基础水溶液中并搅拌；
步骤S3，向步骤S2所得混合中，补充银基础水溶液并搅拌，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15.0-50.0ml/L，石墨烯的质量体积浓度为1.0-20.0g/L。
以下为本发明混合电镀液的具体实施例。
实施例4：
本实施例混合电镀液包括实施例1的复配型分散剂、银基础水溶液和石墨烯；所述银基础水溶液包括KCN和银离子；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；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。
优选的，本实施例混合电镀液的滚镀电流密度为0.6A/dm 2。
优选的，本实施例混合电镀液的挂镀电流密度为0.8A/dm 2。
实施例5：
本实施例混合电镀液包括实施例2的复配型分散剂、银基础水溶液和石墨烯；所述银基础水溶液包括KCN和银离子；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；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。
优选的，本实施例混合电镀液的滚镀电流密度为0.6A/dm 2。
优选的，本实施例混合电镀液的挂镀电流密度为0.8A/dm 2。
实施例6：
本实施例混合电镀液包括实施例2的复配型分散剂、银基础水溶液和石墨烯；所述银基础水溶液包括KCN和银离子；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；所述混合电镀液中，复配型分散剂的体积比浓度为50.0ml/L，石墨烯的质量体积浓度为20.0g/L。
优选的，本实施例混合电镀液的滚镀电流密度为0.5A/dm 2。
优选的，本实施例混合电镀液的挂镀电流密度为0.7A/dm 2。
实施例7：
本实施例混合电镀液包括实施例1的复配型分散剂、银基础水溶液和石墨烯；所述银基础水溶液包括KCN和银离子；所述银基础水溶液中，KCN的质量体积浓度为90g/L，银离子的质量体积浓度为15.0g/L；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。
优选的，本实施例混合电镀液的滚镀电流密度为0.7A/dm 2。
优选的，本实施例混合电镀液的挂镀电流密度为1.0A/dm 2。
实施例8：
本实施例混合电镀液包括实施例3的复配型分散剂、银基础水溶液和石墨烯；所述银基础水溶液包括KCN和银离子；所述银基础水溶液中，KCN的质量体积浓度为150g/L，银离子的质量体积浓度为35.0g/L；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。
优选的，本实施例混合电镀液的滚镀电流密度为0.6A/dm 2。
优选的，本实施例混合电镀液的挂镀电流密度为0.9A/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；所述银基础水溶液包括KCN和银离子；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；所述混合电镀液中，石墨烯的质量体积浓度为2.0g/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。
实施例9：
本实施例复配型分散剂由蒸馏水、非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包括烃基硫酸酯盐化合物和烃基磺酸盐化合物，烃基硫酸酯盐化合物包括2-乙基己基硫酸酯钠盐，烃基磺酸盐化合物包括丁二酸二己酯磺酸钠；所述非离子型表面活性剂为吐温类化合物，吐温类化合物包括吐温-20；所述复配型分散剂中，烃基硫酸酯盐化合物的质量分数为6％，烃基磺酸盐化合物的质量分数为9％，吐温类化合物的质量分数为5％，余量为蒸馏水。
本实施例复配型分散剂制备方法包括以下步骤：
步骤1，向温度为45℃的蒸馏水中，加入烃基硫酸酯盐化合物和吐温类化合物，搅拌8min。
步骤2，将烃基磺酸盐化合物加入步骤1所得混合物中，补充蒸馏水并搅拌12min，制得复配型分散剂。
实施例10：
本实施例复配型分散剂由蒸馏水、非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包括烃基硫酸酯盐化合物和烃基磺酸盐化合物，烃基硫酸酯盐化合物包括2-乙基己基硫酸酯钠盐，烃基磺酸盐化合物包括丁二酸二己酯磺酸钠和二辛基磺化琥珀酸钠；所述非离子型表面活性剂为吐温类化合物，吐温类化合物包括吐温-20；所述复配型分散剂中，烃基硫酸酯盐化合物的质量分数为6％，烃基磺酸盐化合物的质量分数为8％(其中二辛基磺化琥珀酸钠的质量分数为3％，丁二酸二己酯磺酸钠的质量分数为5％)，吐温类化合物的质量分数为6％，余量为蒸馏水。
本实施例复配型分散剂制备方法包括以下步骤：
步骤1，向温度为55℃的蒸馏水中，加入烃基硫酸酯盐化合物和吐温类化合物，搅拌9min。
步骤2，将烃基磺酸盐化合物加入步骤1所得混合物中，补充蒸馏水并搅拌8min，制得复配型分散剂。
实施例11：
本实施例混合电镀液包括实施例9的复配型分散剂、银基础水溶液和石墨烯；所述银基础水溶液包括KCN和银离子；所述银基础水溶液中，KCN的质量体积浓度为170.0g/L，银离子的质量体积浓度为25.0g/L；所述混合电镀液中，复配型分散剂的体积比浓度为20.0ml/L，石墨烯的质量体积浓度为8.0g/L。
优选的，本实施例混合电镀液的滚镀电流密度为0.6A/dm 2。
优选的，本实施例混合电镀液的挂镀电流密度为0.8A/dm 2。
实施例12：
本实施例混合电镀液包括实施例10的复配型分散剂、银基础水溶液和石墨烯；所述银基础水溶液包括KCN和银离子；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；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15.0g/L。
优选的，本实施例混合电镀液的滚镀电流密度为0.7A/dm 2。
优选的，本实施例混合电镀液的挂镀电流密度为0.7A/dm 2。
本实施例还公开一种电镀方法，使用所述混合电镀液为待电镀产品电镀石墨烯-银混合电镀层，具体包括以下操作：对待电镀产品进行清洗，将清洗完成的待电镀产品放入氰化钾溶液进行氰活化，对氰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所述混合电镀液中进行电镀，将电镀产品多次水洗。
表一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，各实施例的电镀产片和空白电镀液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 PCTCN2022084645-appb-000001
Figure PCTCN2022084645-appb-000002
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)，其中使电镀产品的耐磨性能提升5倍以上。
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和润湿剂组成；所述非离子型表面活性剂为吐温类化合物，润湿剂包括烃基硫酸酯盐化合物和烃基磺酸盐化合物。
  2. 根据权利要求1所述的复配型分散剂，其特征在于：所述烃基硫酸酯盐化合物包括2-乙基己基硫酸酯钠盐。
  3. 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，烃基硫酸酯盐化合物的质量分数为5-8％。
  4. 根据权利要求1所述的复配型分散剂，其特征在于：所述烃基磺酸盐化合物包括二辛基磺化琥珀酸钠和丁二酸二己酯磺酸钠中的至少一个。
  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，烃基磺酸盐化合物的质量分数为6-10％。
  6. 根据权利要求1所述的复配型分散剂，其特征在于：所述吐温类化合物包括吐温-20。
  7. 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，吐温类化合物的质量分数为4-6％。
  8. 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，40℃≤T0≤60℃，加入烃基硫酸酯盐化合物和吐温类化合物，并搅拌时间t0，5min≤t0≤10min；
    步骤2，将烃基磺酸盐化合物加入步骤1所得混合物中，补充蒸馏水，并搅拌时间t1，5min≤t1≤15min，制得复配型分散剂。
  9. 一种混合电镀液，其特征在于，其包括权利要求1-7任意一项所述的复配型分散剂、银基础水溶液和石墨烯；所述银基础水溶液包括KCN和银离子。
  10. 根据权利要求9所述的混合电镀液，其特征在于：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。
  11. 根据权利要求9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15.0-50.0ml/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9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 2；
    所述混合电镀液的挂镀电流密度为0.7-1.0A/dm 2。
  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S1，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S2，将权利要求1-7任意一项所述的复配型分散剂、石墨烯加入银基础水溶液中并搅拌；
    步骤S3，向步骤S2所得混合中，补充银基础水溶液并搅拌，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15.0-50.0ml/L，石墨烯的质量体积浓度为1.0-20.0g/L。
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