CN116607134A - 一种pet铜箔、化学镀制备方法及其应用 - Google Patents
一种pet铜箔、化学镀制备方法及其应用 Download PDFInfo
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- CN116607134A CN116607134A CN202310691155.3A CN202310691155A CN116607134A CN 116607134 A CN116607134 A CN 116607134A CN 202310691155 A CN202310691155 A CN 202310691155A CN 116607134 A CN116607134 A CN 116607134A
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- Prior art keywords
- pet film
- copper plating
- electroless copper
- pet
- dopamine
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 238000007747 plating Methods 0.000 title claims abstract description 89
- 239000011889 copper foil Substances 0.000 title claims abstract description 51
- 239000000126 substance Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 90
- 239000010949 copper Substances 0.000 claims abstract description 90
- 229920002799 BoPET Polymers 0.000 claims abstract description 86
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 50
- 229960003638 dopamine Drugs 0.000 claims abstract description 38
- 230000004913 activation Effects 0.000 claims abstract description 31
- 238000005238 degreasing Methods 0.000 claims abstract description 27
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 27
- 229920001690 polydopamine Polymers 0.000 claims abstract description 20
- 229920000587 hyperbranched polymer Polymers 0.000 claims abstract description 17
- 230000004048 modification Effects 0.000 claims abstract description 17
- 238000012986 modification Methods 0.000 claims abstract description 17
- 238000001465 metallisation Methods 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 11
- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 239000004332 silver Substances 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims description 94
- 239000011734 sodium Substances 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 34
- 230000003213 activating effect Effects 0.000 claims description 31
- 238000002791 soaking Methods 0.000 claims description 29
- 101710134784 Agnoprotein Proteins 0.000 claims description 25
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 24
- 238000005202 decontamination Methods 0.000 claims description 24
- 230000003588 decontaminative effect Effects 0.000 claims description 24
- 238000007598 dipping method Methods 0.000 claims description 24
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 24
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 24
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 15
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 13
- 238000002604 ultrasonography Methods 0.000 claims description 13
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 12
- 241000080590 Niso Species 0.000 claims description 12
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 238000007865 diluting Methods 0.000 claims description 12
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005096 rolling process Methods 0.000 claims description 12
- 230000000536 complexating effect Effects 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 230000001678 irradiating effect Effects 0.000 claims description 10
- 238000007772 electroless plating Methods 0.000 claims description 8
- 238000010668 complexation reaction Methods 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052763 palladium Inorganic materials 0.000 abstract description 8
- 238000004132 cross linking Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 230000005855 radiation Effects 0.000 abstract description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- 230000009286 beneficial effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- -1 dopamine quinone compound Chemical class 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- WTDRDQBEARUVNC-LURJTMIESA-N L-DOPA Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-LURJTMIESA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- PQPXZWUZIOASKS-UHFFFAOYSA-N dopaminoquinone Chemical compound NCCC1=CC(=O)C(=O)C=C1 PQPXZWUZIOASKS-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
- C23C18/40—Coating with copper using reducing agents
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1641—Organic substrates, e.g. resin, plastic
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1666—Ultrasonics
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
- C23C18/204—Radiation, e.g. UV, laser
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
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- C—CHEMISTRY; METALLURGY
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/64—Carriers or collectors
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Abstract
一种PET铜箔、化学镀制备方法及其应用，PET铜箔包括PET薄膜，PET薄膜和多巴胺在紫外光的作用下形成聚多巴胺，聚多巴胺经过无钯活化反应后得到交联复合层，交联复合层外侧沉积有银颗粒；活化后的PET薄膜两面覆盖有铜层；制备方法是PET薄膜经除油粗化、在紫外辐射下进行多巴胺自聚合表面改性，在薄膜表面形成紧密附着的交联复合层，和有机‑无机表面建立共价与非共价的相互作用；然后超支化聚合物协助金属沉积无钯活化，最后超声辅助化学镀铜制备PET铜箔；PET铜箔的应用是作为锂离子电池的“集流体”；本发明镀层结合力好，厚度均匀，不仅设备成本低廉，而且工艺性能好，操作简单，经济环保。
Description
技术领域
本发明涉及PET铜箔制备技术领域，具体涉及一种PET铜箔、化学镀制备方法及其应用。
背景技术
铜箔作为锂离子电池的“集流体”，其品质决定锂电池能量密度、电池容量和循环寿命，高安全性和高比能是未来锂电铜箔的发展趋势。PET铜箔采用“三明治”结构，凭借其独特的高分子材料，解决了电池因短路易引发热失控的问题，同时使得电池能量密度提升5％-10％、循环寿命提升5％。PET铜箔具备厚度较薄、用铜量少、兼容性好、安全性高、能量密度大等优势，未来产业规模将不断扩大。
目前，PET铜箔生产工艺(CN217387217U、CN114481080A、CN115058711A)主要采用磁控溅射或真空镀膜使PET金属化，然后采用水电镀方式加厚铜层；由于该工艺所需设备均属于大型精密仪器，且磁控溅射靶材用电量大，蒸镀耗电较高，后续水电镀良品率难控制等原因，故该方法设备成本较高、工艺难度较大。
发明内容
为了克服上述现有技术的缺点，本发明的目的在于提供了一种PET铜箔、化学镀制备方法及其应用，镀层结合力好，厚度均匀，不仅设备成本低廉，而且工艺性能好，操作简单，经济环保。
为了达到上述目的，本发明采取的技术方案为：
一种PET铜箔，包括PET薄膜1，PET薄膜1上设有聚多巴胺4的交联复合层，交联复合层外侧设有银颗粒5；PET薄膜1两面覆盖有铜层。
一种PET铜箔，包括PET薄膜1，PET薄膜1和多巴胺2在紫外光3的作用下形成聚多巴胺4，聚多巴胺4经过无钯活化反应后得到交联复合层，交联复合层外侧沉积有银颗粒5；活化后的PET薄膜两面覆盖有铜层。
一种PET铜箔化学镀制备方法，包括以下步骤：
1)PET薄膜除油去污、微蚀：将PET薄膜放在20-30g/L NaOH、25-35g/L Na2CO3、45-55g/L Na3PO4和1-3g/L SDBS(十二烷基苯磺酸钠)的混合液中于50-65℃下浸泡5-20min后水洗；
2)多巴胺自聚合表面改性：将除油去污、微蚀后的PET薄膜放在含有2-5g/L的盐酸多巴胺溶液中，浸扎处理后进行紫外照射1-3min，重复浸扎照射3-5次，水洗；
3)超支化聚合物协助金属沉积无钯活化：将超支化聚酰胺-胺(HBP-NH2)与AgNO3按络合比13:12～9:8混合，稀释至AgNO3浓度为0.2-4g/L，35℃条件下静置得HBP-NH2/Ag+活化液；将多巴胺自聚合改性后的PET薄膜二浸二扎活化液，轧液率为30-45％，水洗；
4)超声辅助化学镀铜：在超声辅助下将活化后的PET薄膜置于化学镀铜液中进行化学镀铜制备PET铜箔；化学镀铜液温度为55-65℃，pH值为9-11，超声辅助化学镀铜厚度为0.8～4μm。
所用的化学镀铜液组成为：CuSO4·5H2O 5-10g/L，NiSO4·7H2O0.2-1.0g/L，H3BO310-20g/L，Na3H2PO3·H2O 20-40g/L，CHOCOOH·H2O10-20g/L，Na3C6H5O7·2H2O 10-20g/L，三乙醇胺10-20g/L，Na2EDTA 40-50g/L，硫脲或2-巯基苯并噻唑0.1-0.5mg/L，2,2-联吡啶5-15g/L。
一种PET铜箔的应用，作为锂离子电池的“集流体”。
本发明的有益效果为：
1)本发明在紫外辐射下，将多巴胺自聚合表面改性到PET薄膜上，解决了铜层与基体易起皮脱落的问题，多巴胺的邻苯二酚基团易被氧化生成具有邻苯二醌结构的多巴胺醌化合物，多巴胺与多巴胺醌之间发生反歧化反应，生成半醌自由基，之后偶合形成交联键，与此同时在基体表面形成紧密附着的交联复合层；此外，多巴胺表面特殊的官能团结构可以和有机-无机表面建立共价与非共价的相互作用，使交联复合层作为船锚将PET基材和活化金属固定，增强基材与后续镀层的结合力；整个改性过程未添加对环境造成污染的有机溶剂，反应条件温和，步骤简单，易于控制，可使PET表面性质显著改善。
2)本发明利用超支化聚合物协助金属沉积无钯活化替代传统胶体钯法，方法简单易行，沉积金属效果良好。超支化聚合物具有三维准球形的结构，分子中存在大量的伯胺、叔胺、酰胺等官能团，能够对金属产生较好的络合作用，且超支化聚合物具有高溶解性和易成膜等性能，将超支化聚酰胺-胺(HBP-NH2)作为银离子载体制备活化液进行活化，既缩短了工艺流程，又节约了贵金属的用量，且得到的镀层性能更优异。
3)传统以甲醛作为还原剂的化学镀铜法环境污染严重，镀液稳定性较差，且对人伤害极大。本发明以次亚磷酸钠和乙醛酸为还原剂代替甲醛，加入Ni2+作为反应催化剂，在超声辅助下加速铜的自催化沉积，缩短化学镀时间。本发明所制备的PET铜箔成本低廉，操作过程简单，流程短，在工业上易于实现，且经济环保。测试结果表明铜层光亮平整，厚度均匀。
附图说明
图1是实施例PET薄膜多巴胺自聚合改性和无钯活化反应示意图。
具体实施方式
下面结合实施例和附图对本发明做详细描述。
实施例1，一种PET铜箔，包括PET薄膜1，PET薄膜1和多巴胺2在紫外光3的作用下形成聚多巴胺4，聚多巴胺4经过无钯活化反应后得到交联复合层，交联复合层外侧沉积有银颗粒5；活化后的PET薄膜两面覆盖有铜层。
一种PET铜箔化学镀制备方法，包括以下步骤：
1)PET薄膜除油去污、微蚀：将PET薄膜放在25g/L NaOH、30g/L Na2CO3，50g/LNa3PO4和2g/L SDBS(十二烷基苯磺酸钠)的混合液中于60℃下浸泡15min后水洗；
2)多巴胺自聚合表面改性：将除油去污、微蚀后的PET薄膜放在含有2g/L的盐酸多巴胺溶液中，浸扎处理后进行紫外照射3min，重复浸扎照射5次，水洗；
3)超支化聚合物协助金属沉积无钯活化：将超支化聚酰胺-胺(HBP-NH2)与AgNO3按10:9络合比混合，稀释AgNO3浓度为0.6g/L，35℃条件下静置得HBP-NH2/Ag+活化液；将多巴胺自聚合改性后的PET薄膜二浸二扎活化液，轧液率为40％，水洗；
4)超声辅助化学镀铜：在超声辅助下将活化后的PET薄膜置于化学镀铜液中进行化学镀铜制备PET铜箔；化学镀铜液温度为65℃，pH值为10.5，超声辅助化学镀铜厚度为4.0μm；
所用的化学镀铜液的组成为CuSO4·5H2O 8g/L，NiSO4·7H2O 0.8g/L，H3BO3 15g/L，Na3H2PO3·H2O 30g/L，CHOCOOH·H2O 15g/L，Na3C6H5O7·2H2O 15g/L，三乙醇胺15g/L，Na2EDTA 45g/L，硫脲或2-巯基苯并噻唑0.3mg/L，2,2-联吡啶10g/L。
一种PET铜箔的应用，作为锂离子电池的“集流体”。
本实施例的有益效果为：参照图1，PET薄膜1和多巴胺2在紫外光3的作用下形成聚多巴胺4，聚多巴胺4经过无钯活化反应后，活化后沉积有银颗粒5，相关数据如表1所示。
实施例2，一种PET铜箔同实施例1相同。
一种PET铜箔化学镀制备方法，包括以下步骤：
1)PET薄膜除油去污、微蚀：将PET薄膜放在25g/L NaOH、30g/L Na2CO3、50g/LNa3PO4和2g/L SDBS(十二烷基苯磺酸钠)的混合液中于65℃下浸泡5min后水洗；
2)多巴胺自聚合表面改性：将除油去污、微蚀后的PET薄膜放在含有2.5g/L的盐酸多巴胺溶液中，浸扎处理后进行紫外照射2min，重复浸扎照射4次，水洗；
3)超支化聚合物协助金属沉积无钯活化：将超支化聚酰胺-胺(HBP-NH2)与AgNO3按11:10络合比混合，稀释至AgNO3浓度为1.5g/L，35℃条件下静置得HBP-NH2/Ag+活化液；将多巴胺自聚合改性后的PET薄膜二浸二扎活化液，轧液率为45％，水洗；
4)超声辅助化学镀铜：在超声辅助下将活化后的PET薄膜置于化学镀铜液中进行化学镀铜制备PET铜箔；化学镀铜液温度为60℃，pH值为10.5，化学镀铜厚度为2.0μm；；
所用的化学镀铜液的组成为CuSO4·5H2O 8g/L，NiSO4·7H2O 0.8g/L，H3BO3 15g/L，Na3H2PO3·H2O 35g/L，CHOCOOH·H2O 20g/L，Na3C6H5O7·2H2O 20g/L，三乙醇胺20g/L，Na2EDTA 40g/L，硫脲或2-巯基苯并噻唑0.4mg/L，2,2-联吡啶10g/L。
一种PET铜箔的应用，作为锂离子电池的“集流体”。
本实施例的有益效果为：参照图1，PET薄膜1和多巴胺2在紫外光3的作用下形成聚多巴胺4，聚多巴胺4经过无钯活化反应后，活化后沉积有银颗粒5，相关数据如表1所示。
实施例3，一种PET铜箔同实施例1相同。
一种PET铜箔化学镀制备方法，包括以下步骤：
1)PET薄膜除油去污、微蚀：将PET薄膜放在25g/L NaOH、30g/L Na2CO3、50g/LNa3PO4和2g/L SDBS(十二烷基苯磺酸钠)的混合液中于55℃下浸泡15min后水洗；
2)多巴胺自聚合表面改性：将除油去污、微蚀后的PET薄膜放在含有3g/L的盐酸多巴胺溶液中，浸扎处理后进行紫外照射2min，重复浸扎照射3次，水洗；
3)超支化聚合物协助金属沉积无钯活化：将超支化聚酰胺-胺(HBP-NH2)与AgNO3按12:11络合比混合，稀释至AgNO3浓度为2.4g/L，35℃条件下静置得HBP-NH2/Ag+活化液；将多巴胺自聚合改性后的PET薄膜二浸二扎活化液，轧液率为35％，水洗；
4)超声辅助化学镀铜：在超声辅助下将活化后的PET薄膜置于化学镀铜液中进行化学镀铜制备PET铜箔；化学镀铜液温度为60℃，使用pH值为11，化学镀铜厚度为1.5μm；
所用的化学镀铜液的组成为CuSO4·5H2O 10g/L，NiSO4·7H2O1.0g/L，H3BO3 20g/L，Na3H2PO3·H2O 40g/L，CHOCOOH·H2O 20g/L，Na3C6H5O7·2H2O 20g/L，三乙醇胺20g/L，Na2EDTA 50g/L，硫脲或2-巯基苯并噻唑0.3mg/L，2,2-联吡啶15g/L。
一种PET铜箔的应用，作为锂离子电池的“集流体”。
本实施例的有益效果为：参照图1，PET薄膜1和多巴胺2在紫外光3的作用下形成聚多巴胺4，聚多巴胺4经过无钯活化反应后，活化后沉积有银颗粒5，相关数据如表1所示。
实施例4，一种PET铜箔同实施例1相同。
一种PET铜箔化学镀制备方法，包括以下步骤：
1)PET薄膜除油去污、微蚀：将PET薄膜放在20g/L NaOH、25g/L Na2CO3、45g/LNa3PO4和1g/L SDBS(十二烷基苯磺酸钠)的混合液中于50℃下浸泡20min后水洗；
2)多巴胺自聚合表面改性：将除油去污、微蚀后的PET薄膜放在含有2g/L的盐酸多巴胺溶液中，浸扎处理后进行紫外照射1min，重复浸扎照射3次，水洗；
3)超支化聚合物协助金属沉积无钯活化：将超支化聚酰胺-胺(HBP-NH2)与AgNO3按9:8络合比混合，稀释至AgNO3浓度为3.2g/L，35℃条件下静置得HBP-NH2/Ag+活化液；将多巴胺自聚合改性后的PET薄膜二浸二扎活化液，轧液率为30％，水洗；
4)超声辅助化学镀铜：在超声辅助下将活化后的PET薄膜置于化学镀铜液中进行化学镀铜制备PET铜箔；化学镀铜液温度为55℃，pH值为9，超声辅助化学镀铜厚度为0.8μm；。
所用的化学镀铜液组成为：CuSO4·5H2O 5g/L，NiSO4·7H2O0.2g/L，H3BO3 10g/L，Na3H2PO3·H2O 20g/L，CHOCOOH·H2O 10g/L，Na3C6H5O7·2H2O 10g/L，三乙醇胺10g/L，Na2EDTA 40g/L，硫脲或2-巯基苯并噻唑0.1mg/L，2,2-联吡啶5g/L。
一种PET铜箔的应用，作为锂离子电池的“集流体”。
本实施例的有益效果为：参照图1，PET薄膜1和多巴胺2在紫外光3的作用下形成聚多巴胺4，聚多巴胺4经过无钯活化反应后，活化后沉积有银颗粒5，相关数据如表1所示。
实施例5，一种PET铜箔同实施例1相同。
一种PET铜箔化学镀制备方法，包括以下步骤：
1)PET薄膜除油去污、微蚀：将PET薄膜放在30g/L NaOH、35g/L Na2CO3，55g/LNa3PO4和3g/L SDBS(十二烷基苯磺酸钠)的混合液中于60℃下浸泡10min后水洗；
2)多巴胺自聚合表面改性：将除油去污、微蚀后的PET薄膜放在含有5g/L的盐酸多巴胺溶液中，浸扎处理后进行紫外照射3min，重复浸扎照射5次，水洗；
3)超支化聚合物协助金属沉积无钯活化：将超支化聚酰胺-胺(HBP-NH2)与AgNO3按10:9络合比混合，稀释至AgNO3浓度为4g/L，35℃条件下静置得HBP-NH2/Ag+活化液；将多巴胺自聚合改性后的PET薄膜二浸二扎活化液，轧液率为40％，水洗；
4)超声辅助化学镀铜：在超声辅助下将活化后的PET薄膜置于化学镀铜液中进行化学镀铜制备PET铜箔；化学镀铜液温度为65℃，pH值为11，超声辅助化学镀铜厚度为3.0μm；
所用的化学镀铜液的组成为CuSO4·5H2O 8g/L，NiSO4·7H2O 0.8g/L，H3BO3 15g/L，Na3H2PO3·H2O 30g/L，CHOCOOH·H2O 15g/L，Na3C6H5O7·2H2O 15g/L，三乙醇胺15g/L，Na2EDTA45g/L，硫脲或2-巯基苯并噻唑0.3mg/L，2,2-联吡啶10g/L。
一种PET铜箔的应用，作为锂离子电池的“集流体”。
本实施例的有益效果为：参照图1，PET薄膜1和多巴胺2在紫外光3的作用下形成聚多巴胺4，聚多巴胺4经过无钯活化反应后，活化后沉积有银颗粒5，相关数据如表1所示。
对比例1：采用实施例1的除油微蚀方法对PET薄膜进行预处理，粗化后采用传统胶体钯法进行活化，最后采用传统甲醛作为还原剂进行化学镀铜；粗化液组成为4％K2Cr2O7和80％H2SO4的混合溶液，60℃粗化20min；活化液组成为1.5g/L Pd，25g/L Sn和250ml/L HCl的水溶液，室温活化处理15min；化学镀铜液组成为6ml/L甲醛(37％)，24g/L Na2EDTA，CuSO4·5H2O 15g/L，28g/L NaOH。
对比例2：采用实施例2的除油微蚀方法对PET薄膜进行预处理，粗化后采用无钯活化法进行敏化活化，最后采用传统甲醛作为还原剂进行化学镀铜；粗化液组成为4％K2Cr2O7和80％H2SO4的混合溶液，60℃粗化20min；敏化液组成20g/L SnCl2，45ml/L浓HCl和少量锡粒，室温敏化处理5min；活化液组成为4g/L AgNO3滴加NH4OH至溶液透明，室温活化10min；化学镀铜液组成为6ml/L甲醛(37％)，24g/L Na3C6H5O7·2H2O，CuSO4·5H2O 15g/L，28g/LNaOH。
从表1中对比例1、2及实施例1-5的数据中可知，多巴胺自聚合表面改性、超支化聚合物协助金属沉积无钯活化以及超声辅助化学镀铜等方式的应用，极大的提升了镀层厚度的均匀性、降低了PET薄膜的电阻率。
表1
| 实施例 | 厚度均匀性/μm | 电阻率/μΩ·cm |
| 对比例1 | ±0.87 | 85 |
| 对比例2 | ±0.95 | 102 |
| 实施例1 | ±0.05 | 3 |
| 实施例2 | ±0.09 | 8 |
| 实施例3 | ±0.12 | 10 |
| 实施例4 | ±0.15 | 15 |
| 实施例5 | ±0.07 | 5 |
Claims (10)
1.一种PET铜箔，其特征在于：包括PET薄膜(1)，PET薄膜(1)上设有聚多巴胺(4)的交联复合层，交联复合层外侧设有银颗粒(5)；PET薄膜(1)两面覆盖有铜层。
2.一种PET铜箔，其特征在于：包括PET薄膜(1)，PET薄膜(1)和多巴胺(2)在紫外光(3)的作用下形成聚多巴胺(4)，聚多巴胺(4)经过无钯活化反应后得到交联复合层，交联复合层外侧沉积有银颗粒(5)；活化后的PET薄膜两面覆盖有铜层。
3.权利要求2所述的一种PET铜箔化学镀制备方法，其特征在于，包括以下步骤：
1)PET薄膜除油去污、微蚀：将PET薄膜放在20-30g/L NaOH、25-35g/L Na2CO3、45-55g/LNa3PO4和1-3g/L SDBS(十二烷基苯磺酸钠)的混合液中于50-65℃下浸泡5-20min后水洗；
2)多巴胺自聚合表面改性：将除油去污、微蚀后的PET薄膜放在含有2-5g/L的盐酸多巴胺溶液中，浸扎处理后进行紫外照射1-3min，重复浸扎照射3-5次，水洗；
3)超支化聚合物协助金属沉积无钯活化：将超支化聚酰胺-胺(HBP-NH2)与AgNO3按络合比13:12～9:8混合，稀释至AgNO3浓度为0.2-4g/L，35℃条件下静置得HBP-NH2/Ag+活化液；将多巴胺自聚合改性后的PET薄膜二浸二扎活化液，轧液率为30-45％，水洗；
4)超声辅助化学镀铜：在超声辅助下将活化后的PET薄膜置于化学镀铜液中进行化学镀铜制备PET铜箔；化学镀铜液温度为55-65℃，pH值为9-11，超声辅助化学镀铜厚度为0.8～4μm。
4.根据权利要求3所述的方法，其特征在于，所用的化学镀铜液组成为：CuSO4·5H2O 5-10g/L，NiSO4·7H2O 0.2-1.0g/L，H3BO310-20g/L，Na3H2PO3·H2O 20-40g/L，CHOCOOH·H2O10-20g/L，Na3C6H5O7·2H2O 10-20g/L，三乙醇胺10-20g/L，Na2EDTA 40-50g/L，硫脲或2-巯基苯并噻唑0.1-0.5mg/L，2,2-联吡啶5-15g/L。
5.根据权利要求4所述的方法，其特征在于，包括以下步骤：
1)PET薄膜除油去污、微蚀：将PET薄膜放在25g/L NaOH、30g/L Na2CO3，50g/L Na3PO4和2g/L SDBS(十二烷基苯磺酸钠)的混合液中于60℃下浸泡15min后水洗；
2)多巴胺自聚合表面改性：将除油去污、微蚀后的PET薄膜放在含有2g/L的盐酸多巴胺溶液中，浸扎处理后进行紫外照射3min，重复浸扎照射5次，水洗；
3)超支化聚合物协助金属沉积无钯活化：将超支化聚酰胺-胺(HBP-NH2)与AgNO3按10:9络合比混合，稀释AgNO3浓度为0.6g/L，35℃条件下静置得HBP-NH2/Ag+活化液；将多巴胺自聚合改性后的PET薄膜二浸二扎活化液，轧液率为40％，水洗；
4)超声辅助化学镀铜：在超声辅助下将活化后的PET薄膜置于化学镀铜液中进行化学镀铜制备PET铜箔；化学镀铜液温度为65℃，pH值为10.5，超声辅助化学镀铜厚度为4.0μm；
所用的化学镀铜液的组成为CuSO4·5H2O 8g/L，NiSO4·7H2O 0.8g/L，H3BO3 15g/L，Na3H2PO3·H2O 30g/L，CHOCOOH·H2O 15g/L，Na3C6H5O7·2H2O 15g/L，三乙醇胺15g/L，Na2EDTA45g/L，硫脲或2-巯基苯并噻唑0.3mg/L，2,2-联吡啶10g/L。
6.根据权利要求4所述的方法，其特征在于，包括以下步骤：
1)PET薄膜除油去污、微蚀：将PET薄膜放在25g/L NaOH、30g/L Na2CO3、50g/L Na3PO4和2g/L SDBS(十二烷基苯磺酸钠)的混合液中于65℃下浸泡5min后水洗；
2)多巴胺自聚合表面改性：将除油去污、微蚀后的PET薄膜放在含有2.5g/L的盐酸多巴胺溶液中，浸扎处理后进行紫外照射2min，重复浸扎照射4次，水洗；
3)超支化聚合物协助金属沉积无钯活化：将超支化聚酰胺-胺(HBP-NH2)与AgNO3按11:10络合比混合，稀释至AgNO3浓度为1.5g/L，35℃条件下静置得HBP-NH2/Ag+活化液；将多巴胺自聚合改性后的PET薄膜二浸二扎活化液，轧液率为45％，水洗；
4)超声辅助化学镀铜：在超声辅助下将活化后的PET薄膜置于化学镀铜液中进行化学镀铜制备PET铜箔；化学镀铜液温度为60℃，pH值为10.5，化学镀铜厚度为2.0μm；；
所用的化学镀铜液的组成为CuSO4·5H2O 8g/L，NiSO4·7H2O 0.8g/L，H3BO3 15g/L，Na3H2PO3·H2O 35g/L，CHOCOOH·H2O 20g/L，Na3C6H5O7·2H2O 20g/L，三乙醇胺20g/L，Na2EDTA 40g/L，硫脲或2-巯基苯并噻唑0.4mg/L，2,2-联吡啶10g/L。
7.根据权利要求4所述的方法，其特征在于，包括以下步骤：
1)PET薄膜除油去污、微蚀：将PET薄膜放在25g/L NaOH、30g/L Na2CO3、50g/L Na3PO4和2g/L SDBS(十二烷基苯磺酸钠)的混合液中于55℃下浸泡15min后水洗；
2)多巴胺自聚合表面改性：将除油去污、微蚀后的PET薄膜放在含有3g/L的盐酸多巴胺溶液中，浸扎处理后进行紫外照射2min，重复浸扎照射3次，水洗；
3)超支化聚合物协助金属沉积无钯活化：将超支化聚酰胺-胺(HBP-NH2)与AgNO3按12:11络合比混合，稀释至AgNO3浓度为2.4g/L，35℃条件下静置得HBP-NH2/Ag+活化液；将多巴胺自聚合改性后的PET薄膜二浸二扎活化液，轧液率为35％，水洗；
4)超声辅助化学镀铜：在超声辅助下将活化后的PET薄膜置于化学镀铜液中进行化学镀铜制备PET铜箔；化学镀铜液温度为60℃，使用pH值为11，化学镀铜厚度为1.5μm；
所用的化学镀铜液的组成为CuSO4·5H2O 10g/L，NiSO4·7H2O1.0g/L，H3BO3 20g/L，Na3H2PO3·H2O 40g/L，CHOCOOH·H2O 20g/L，Na3C6H5O7·2H2O 20g/L，三乙醇胺20g/L，Na2EDTA 50g/L，硫脲或2-巯基苯并噻唑0.3mg/L，2,2-联吡啶15g/L。
8.根据权利要求4所述的方法，其特征在于，包括以下步骤：
1)PET薄膜除油去污、微蚀：将PET薄膜放在20g/L NaOH、25g/L Na2CO3、45g/L Na3PO4和1g/L SDBS(十二烷基苯磺酸钠)的混合液中于50℃下浸泡20min后水洗；
2)多巴胺自聚合表面改性：将除油去污、微蚀后的PET薄膜放在含有2g/L的盐酸多巴胺溶液中，浸扎处理后进行紫外照射1min，重复浸扎照射3次，水洗；
3)超支化聚合物协助金属沉积无钯活化：将超支化聚酰胺-胺(HBP-NH2)与AgNO3按9:8络合比混合，稀释至AgNO3浓度为3.2g/L，35℃条件下静置得HBP-NH2/Ag+活化液；将多巴胺自聚合改性后的PET薄膜二浸二扎活化液，轧液率为30％，水洗；
4)超声辅助化学镀铜：在超声辅助下将活化后的PET薄膜置于化学镀铜液中进行化学镀铜制备PET铜箔；化学镀铜液温度为55℃，pH值为9，超声辅助化学镀铜厚度为0.8μm；。
所用的化学镀铜液组成为：CuSO4·5H2O 5g/L，NiSO4·7H2O0.2g/L，H3BO3 10g/L，Na3H2PO3·H2O 20g/L，CHOCOOH·H2O 10g/L，Na3C6H5O7·2H2O 10g/L，三乙醇胺10g/L，Na2EDTA 40g/L，硫脲或2-巯基苯并噻唑0.1mg/L，2,2-联吡啶5g/L。
9.根据权利要求4所述的方法，其特征在于，包括以下步骤：
1)PET薄膜除油去污、微蚀：将PET薄膜放在30g/L NaOH、35g/L Na2CO3，55g/L Na3PO4和3g/L SDBS(十二烷基苯磺酸钠)的混合液中于60℃下浸泡10min后水洗；
2)多巴胺自聚合表面改性：将除油去污、微蚀后的PET薄膜放在含有5g/L的盐酸多巴胺溶液中，浸扎处理后进行紫外照射3min，重复浸扎照射5次，水洗；
3)超支化聚合物协助金属沉积无钯活化：将超支化聚酰胺-胺(HBP-NH2)与AgNO3按10:9络合比混合，稀释至AgNO3浓度为4g/L，35℃条件下静置得HBP-NH2/Ag+活化液；将多巴胺自聚合改性后的PET薄膜二浸二扎活化液，轧液率为40％，水洗；
4)超声辅助化学镀铜：在超声辅助下将活化后的PET薄膜置于化学镀铜液中进行化学镀铜制备PET铜箔；化学镀铜液温度为65℃，pH值为11，超声辅助化学镀铜厚度为3.0μm；；
所用的化学镀铜液的组成为CuSO4·5H2O 8g/L，NiSO4·7H2O 0.8g/L，H3BO3 15g/L，Na3H2PO3·H2O 30g/L，CHOCOOH·H2O 15g/L，Na3C6H5O7·2H2O 15g/L，三乙醇胺15g/L，Na2EDTA 45g/L，硫脲或2-巯基苯并噻唑0.3mg/L，2,2-联吡啶10g/L。
10.权利要求1-9所述的一种PET铜箔的应用，其特征在于，作为锂离子电池的“集流体”。
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