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CN-122013272-A - HVLP copper foil electroplating process

CN122013272ACN 122013272 ACN122013272 ACN 122013272ACN-122013272-A

Abstract

The invention discloses an HVLP copper foil electroplating process which comprises the following steps of S1, selecting a substrate, taking a 12 mu m high-purity battery foil as an electroplating substrate, S2, adding a DMPS-collagen-ionic liquid functionalized graphene (IL-Gr) composite additive into electroplating liquid, S3, combining an HVLP spraying technology with electroplating, spraying electroplating liquid containing the additive in the step S2 on the surface of a copper foil in an atomizing manner through an array nozzle, and sequentially carrying out pretreatment, HVLP atomization spraying roughening-curing electroplating, alloying treatment, silane coupling agent treatment and drying to obtain the HVLP copper foil. The HVLP copper foil prepared by the method has the advantages that the double-sided roughness (Rz) is less than or equal to 1.0 mu m, the peel strength is more than or equal to 0.6N/mm, the tensile strength is more than or equal to 300MPa, the elongation is more than or equal to 6%, the plating layer has no pinholes and knots, the uniformity deviation is less than or equal to +/-3%, meanwhile, the process improves the utilization rate of the electroplating solution, reduces the grain size of the copper foil to below 0.2 mu m, improves the twin boundary density to above 23%, obviously enhances the compactness of a dendritic copper structure, and avoids falling off in subsequent processing.

Inventors

  • CHEN XIAODONG
  • FU ZHENGBING
  • WANG WEI
  • Tong Kaiwen
  • Zhong Fuqi
  • DONG JIANPING
  • TAO JUN
  • CHEN YANXIA
  • ZHANG XIN

Assignees

  • 江西鑫铂瑞科技股份有限公司

Dates

Publication Date
20260512
Application Date
20260228

Claims (8)

  1. 1. An HVLP copper foil electroplating process is characterized by comprising the following steps: s1, selecting a substrate, namely taking a 12 mu m high-purity battery foil as an electroplating substrate; s2, adding a DMPS-collagen-ionic liquid functionalized graphene (IL-Gr) composite additive into the electroplating solution; S3, combining an HVLP spraying technology with electroplating, spraying the electroplating solution containing the additive in the step S2 on the surface of the copper foil in an atomizing mode through an array nozzle, and sequentially carrying out pretreatment, HVLP atomization spraying roughening-curing electroplating, alloying treatment, silane coupling agent treatment and drying to obtain the HVLP copper foil; Wherein, when HVLP atomization spraying coarsening-solidification electroplating, gradient current density and plating liquid flow rate are synchronously controlled.
  2. 2. The HVLP copper foil electroplating process of claim 1, wherein in the step S3, the spraying pressure is 0.2-1.0 bar, the atomization flow is 600-1500L/min, the distance between the nozzle and the surface of the copper foil is 15-20 cm, the atomization particle size of the electroplating solution is 50-100 μm, the nozzles are uniformly distributed in an array mode, and the distance between adjacent nozzles is 5-10 cm.
  3. 3. The HVLP copper foil electroplating process of claim 1, wherein in step S2, the DMPS-collagen-ionic liquid functionalized graphene (IL-Gr) composite additive is added at a concentration of 10-15 mg/L of 2, 3-dimercapto-1-propanesulfonate (DMPS), 8-10 mg/L of collagen, 0.2-0.3 g/L of ionic liquid functionalized graphene (IL-Gr), and 0.4-0.5 g/L of chloride ions and 0.4-0.5 g/L of sodium molybdate are added as auxiliary additives.
  4. 4. The HVLP copper foil electroplating process of claim 1, wherein in step S3, the pretreatment comprises single-sided matte molding, acid washing and water washing; The pickling solution is a sulfuric acid system, the concentration of copper ions is less than or equal to 10g/L, the concentration of sulfuric acid is 90+/-10 g/L, the pickling temperature is 35+/-2 ℃, the spraying flow of a pickling tank HVLP is 8+/-0.5 m 3 /h, and the pickling time is 3-5 min.
  5. 5. The HVLP copper foil electroplating process of claim 1, wherein in step S3, during roughening electroplating, the concentration of copper ions in the electroplating solution is 25+ -0.5 g/L, the concentration of sulfuric acid is 95+ -10 g/L, the treatment temperature is 25-30 ℃, the HVLP spraying flow is 8+ -0.5 m 3 /h, the roughening current is 2700-3100A, the current density is 18-22A/dm 2 , the roughening time is 2-4 min, and 1-2 roughening-curing cycles are repeated after the roughening is completed.
  6. 6. The HVLP copper foil electroplating process of claim 1, wherein in step S3, during solidification and electroplating, the concentration of copper ions in the electroplating solution is 45+ -5 g/L, the concentration of sulfuric acid is 90+ -2.5 g/L, the treatment temperature is 50+ -2 ℃, the HVLP spraying flow is 11+ -0.5 m 3 /h, the solidification current is 1400+ -50A, the current density at the liquid inlet end of the electroplating tank is 20+ -1A/dm 2 , the current density at the liquid outlet end is 16+ -1A/dm 2 , and the solidification time is 1-2 min.
  7. 7. The HVLP copper foil electroplating process of claim 1, wherein in step S3, the alloying treatment is nickel plating, zinc plating and chromium plating in sequence; Wherein, nickel ions in the nickel plating solution are 0.36+/-0.5 g/L, cobalt ions are 0.64+/-0.5 g/L, potassium pyrophosphate is 40+/-2 g/L, the temperature is 40+/-1 ℃, the pH is 10.0+/-0.2, the HVLP spraying flow is 6+/-0.5 m 3 /h, the current density of a treatment surface is 5+/-0.5A/dm 2 , and the current density of a non-treatment surface is 6+/-0.5A/dm 2 .
  8. 8. The HVLP copper foil electroplating process of claim 1, wherein in step S3, the drying treatment is sectional hot air drying, the temperature of the first stage is 60+/-5 ℃, the temperature of the second stage is 80+/-5 ℃, the total drying time is 5-8 min, and the water content of the dried copper foil is less than or equal to 0.05%.

Description

HVLP copper foil electroplating process Technical Field The invention relates to the technical field of copper foil electroplating, in particular to an HVLP copper foil electroplating process. Background The HVLP copper foil is used as a standard material of a circuit board, the conventional HVLP copper foil electroplating process mostly adopts immersion type electrodeposition, the additive in a roughening stage is single, low roughness and high peeling strength of the copper foil cannot be balanced through microelement regulation and control such as chloridion, molybdate and the like, when the roughness is reduced to below 1 mu m, the peeling strength of the copper foil and a resin substrate is lower than 0.5N/mm, copper ions of immersion type electroplating are not supplemented uniformly, concentration difference in a groove causes pinholes and nodulation of a plating layer, uniformity deviation exceeds +/-5%, and the prior art can solve the problem of uneven distribution of electroplating liquid. For this reason, we propose an HVLP copper foil electroplating process to solve the above problems. Disclosure of Invention The invention aims to provide an HVLP copper foil electroplating process for solving the problems in the prior art. In order to achieve the above purpose, the present invention provides the following technical solutions: an HVLP copper foil electroplating process comprising the steps of: s1, selecting a substrate, namely taking a 12 mu m high-purity battery foil as an electroplating substrate, wherein the purity of the battery foil is more than or equal to 99.99%, the surface evenness is high, the longitudinal and transverse ductility is excellent, and the copper foil is prevented from being stretched and broken in the electroplating process; s2, adding a DMPS-collagen-ionic liquid functionalized graphene (IL-Gr) composite additive into the electroplating solution; Wherein, DMPS forms firm covalent bond with copper to realize long-acting grain refinement, collagen inhibits copper deposition through amino to further reduce roughness, IL-Gr as nano template refines copper grain and densifies twin crystal boundary, balance low roughness and high peel strength; S3, combining an HVLP spraying technology with electroplating, spraying the electroplating solution containing the additive in the step S2 on the surface of the copper foil in an atomizing manner through an array nozzle, ensuring uniform distribution of copper ions, improving the uniformity of a plating layer, simultaneously improving the utilization rate of the electroplating solution to more than 80%, and then sequentially carrying out pretreatment, HVLP atomization spraying coarsening-curing electroplating, alloying treatment, silane coupling agent treatment and drying to obtain the HVLP copper foil; The HVLP atomization spraying coarsening-solidifying electroplating method is characterized in that when in HVLP atomization spraying coarsening-solidifying electroplating, gradient current density and plating solution flow rate are synchronously controlled, high current density at the liquid inlet end of the electroplating bath realizes quick nucleation, low current density at the liquid outlet end realizes smooth growth of crystal grains, and meanwhile, the gradient plating solution flow rate is matched, so that real-time replenishment of copper ions is ensured, and compactness of a dendritic copper structure is enhanced. The continuous tape-running production is adopted, the copper foil tape-running speed is 15-18 m/min, the whole electroplating process is monitored by adopting online optics, the HVLP spraying parameters and the current density are regulated and controlled in real time, and the plating uniformity is ensured. Further, in the step S3, during spraying, the spraying pressure is 0.2-1.0 bar, the atomization flow is 600-1500L/min, the distance between the nozzle and the surface of the copper foil is 15-20 cm, the atomization particle size of the electroplating solution is 50-100 mu m, the nozzles are uniformly distributed in an array mode, and the distance between adjacent nozzles is 5-10 cm. Further, in the step S2, the DMPS-collagen-ionic liquid functionalized graphene (IL-Gr) composite additive is added at the concentration of 10-15 mg/L of 2, 3-dimercapto-1-propanesulfonate (DMPS), 8-10 mg/L of collagen and 0.2-0.3 g/L of ionic liquid functionalized graphene (IL-Gr), and 0.4-0.5 g/L of chloride ions and 0.4-0.5 g/L of sodium molybdate are added as auxiliary additives. Further, in the step S3, the pretreatment includes single-sided rough surface molding, acid washing and water washing; The pickling solution is a sulfuric acid system, the concentration of copper ions is less than or equal to 10g/L, the concentration of sulfuric acid is 90+/-10 g/L, the pickling temperature is 35+/-2 ℃, the spraying flow of a pickling tank HVLP is 8+/-0.5 m 3/h, and the pickling time is 3-5 min. Further, in the step S3, during roughening pl