CN110636693A - Method for electroplating graphene-metal composite material coating by using complex pulse, PCB and motor - Google Patents
Method for electroplating graphene-metal composite material coating by using complex pulse, PCB and motor Download PDFInfo
- Publication number
- CN110636693A CN110636693A CN201810646051.XA CN201810646051A CN110636693A CN 110636693 A CN110636693 A CN 110636693A CN 201810646051 A CN201810646051 A CN 201810646051A CN 110636693 A CN110636693 A CN 110636693A
- Authority
- CN
- China
- Prior art keywords
- graphene
- ionic liquid
- ions
- current
- period
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002905 metal composite material Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 53
- 238000000576 coating method Methods 0.000 title claims abstract description 42
- 239000011248 coating agent Substances 0.000 title claims abstract description 36
- 238000009713 electroplating Methods 0.000 title claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 74
- 239000002608 ionic liquid Substances 0.000 claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000758 substrate Substances 0.000 claims abstract description 36
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 28
- 238000000151 deposition Methods 0.000 claims abstract description 24
- 238000007747 plating Methods 0.000 claims abstract description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 54
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 33
- 229910052802 copper Inorganic materials 0.000 claims description 33
- 239000010949 copper Substances 0.000 claims description 33
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 30
- 229910001431 copper ion Inorganic materials 0.000 claims description 30
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 24
- 235000019743 Choline chloride Nutrition 0.000 claims description 24
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 24
- 229960003178 choline chloride Drugs 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 21
- -1 gallium ions Chemical class 0.000 claims description 20
- 230000008021 deposition Effects 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910052733 gallium Inorganic materials 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001430 chromium ion Inorganic materials 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910001449 indium ion Inorganic materials 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 238000007639 printing Methods 0.000 abstract description 2
- 238000004804 winding Methods 0.000 abstract description 2
- 238000001237 Raman spectrum Methods 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 8
- 150000002500 ions Chemical group 0.000 description 7
- 238000004070 electrodeposition Methods 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005411 Van der Waals force Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- 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
- C25D3/66—Electroplating: Baths therefor from melts
- C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/061—Etching masks
Abstract
The invention relates to the technical field of material surface engineering, and provides a method for electroplating a graphene-metal composite material coating by using complex pulses, a PCB (printed circuit board) and a motor. The method specifically comprises the steps of taking an ionic liquid as an electroplating solution, wherein graphene oxide is dispersed in the ionic liquid, and the ionic liquid also contains metal ions; and depositing a graphene-metal composite material coating on the cathode substrate by current or voltage control pulses, wherein the current or voltage control pulses comprise a forward pulse period, a reverse pulse period and a pause period. The method has simple process and low cost, does not have the environmental pollution of the traditional electroplating, and can be applied to the production of large-area coatings or films. The PCB comprises a substrate plate and a bottom layer conductive wire, and the graphene-metal composite plating layer and the conductive wire are manufactured by the method. The invention also discloses a novel motor which is formed by printing and winding the graphene-containing conductive wire on a PCB (printed Circuit Board) to form a brushless motor stator.
Description
Technical Field
The invention relates to the technical field of material surface engineering, in particular to a method for electroplating a graphene-metal composite material coating by using complex pulses, a PCB manufactured by using the method, and a motor using the PCB.
Background
Graphene is an ultra-thin graphite containing only a single atomic layer or a few atomic layers, each atomic layer consisting of sp2The hybridized carbon atoms form a regular hexagonal lattice, a honeycomb two-dimensional structure, and were first prepared and characterized in 2004 by Kostya Novoselov and Andre Geim, university of manchester, england, using a simple method known as mechanical microstress technology.
Graphene is the highest strength substance known to humans, and has many novel physical properties. Graphene is the best material known at present for conducting at normal temperature, and the conductivity of graphene far exceeds that of a common conductor. In addition, graphene can be used to produce composite materials which have been used in the production of batteries/supercapacitors, hydrogen storage, photovoltaic devices and systems, sensors, etc. The graphene composite metal material is prepared by adding a small amount of graphene into a metal material, so that the conductivity and other properties of the metal material are optimized at low cost.
At present, a plurality of methods for preparing graphene composite metal materials are available, wherein a bulk casting and pressing workpiece can be prepared by adopting a powder sintering technology and then pressed into sheets, for example, a patent with the publication number of CN 104264000B provides a graphene modified high-heat-conductivity aluminum-based composite material and a powder metallurgy preparation method thereof, and for example, a patent in the pending publication number of CN201611082597.4 provides a high-electric-conductivity graphene/copper-based layered composite material and a preparation method thereof, wherein the latter comprises the steps of firstly wrapping metal copper nano powder by a chemical vapor deposition method and then sintering the metal copper nano powder into a compact block by powder sintering. Although plates and pipes made by this type of technique are widely used, they are not suitable for applications requiring large area coatings or films.
Chemical vapor deposition methods commonly used for preparing large-area thin films are also adopted for preparing copper/graphene/copper multilayer composite films, such as "Strength characterization effect of single-atomic-layer graphene atomic-layer composites" (Nature Communication 4, 2114(2013)) of Kim and "Thermal properties of graphene-coppers-graphene multilayer composites" (Nano Letters 14,1497(2014)) of Goli. However, the preparation method has high cost, complex process and needs high-temperature high-vacuum and other preparation environments, so that large-area industrial production of the graphene composite metal material is not realized.
Electroplating methods widely used for producing metal Thin and thick Films are also used to trial produce graphene composite metal coatings, such as those provided by Jagannadham "Thermal conductivity of Copper-graphene composite plated Films" (Metal. Mater. Trans. B43, 316(2012)), Maharana "Surface-mechanical and electrical properties of plated Copper-graphene oxide composite plated Films" (J. Mater. Sci.52, 2019 (2017)) and Raghupath "Copper-graphene oxide composite plated Films for coating Films" (NaCl 3, 636% NaCl). In addition, for example, the pending patent publication No. CN 201410848015.3 provides an aluminum-based copper-plated graphene thin film composite material with high thermal conductivity and a preparation method thereof, the pending patent publication No. CN 201710247094.6 provides a method for preparing a graphene/copper composite material by using aerobic sintering, and the pending patent publication No. CN 201710680997.3 provides a reduced graphene oxide-copper composite coating and a preparation method and application thereof. Although the methods can deposit the graphene composite copper coating, the traditional water-based electroplating is adopted, the development of the method is limited due to environmental pollution, graphene oxide needs to be deposited and converted into reduced graphene in the water-based metal electroplating process, and hydrogen is prevented from being released by electrolysis of water, so far, the difficulties can not be overcome by the practical production technology.
Disclosure of Invention
The invention aims to provide a method for electroplating a graphene-metal composite material coating by using complex pulses, a PCB manufactured by using the method, and an application of the PCB to a motor. The method has simple process and lower cost, does not relate to the problem of environmental pollution, and can be applied to the production of large-area coatings or films.
In order to achieve the purpose, the invention provides the following technical scheme:
in one aspect, an embodiment of the present invention provides a method for electroplating a graphene-metal composite plating layer by using a complex pulse, where the method includes:
taking an ionic liquid as an electroplating liquid, wherein graphene oxide is dispersed in the ionic liquid, and the ionic liquid also contains metal ions;
depositing a graphene-metal composite material coating on a cathode substrate by a current control pulse, wherein the current control pulse comprises a positive pulse period when current and voltage are negative on a deposition surface, a reverse pulse period when current and voltage are positive on the deposition surface, and a period comprising one or more of the following a-c, a pause period when the current is zero, b period when the current is negative and the voltage is positive, c period when the current is positive and the voltage is negative; alternatively, the first and second electrodes may be,
and depositing a graphene-metal composite coating on the cathode substrate by a voltage control pulse, wherein the voltage control pulse comprises a positive pulse period when the voltage and the current are negative on the deposition surface, a reverse pulse period when the voltage and the current are positive on the deposition surface, and a period comprising one or more of d-f, a pause period when the d voltage is zero, a period when the e voltage is negative and the current is positive, and a period when the f voltage is positive and the current is negative.
In the technical scheme, during the pause period, the graphene oxide is adsorbed on the surface of the cathode substrate by Van der Waals force; in a forward pulse period, graphene oxide adsorbed on the surface of a cathode substrate releases an oxidation functional group and is firstly reduced into graphene, then metal ions in ionic liquid are reduced on the cathode substrate, and the reduced graphene oxide and the metal ions form a graphene-metal composite material coating on the surface of the cathode substrate; in the reverse pulse period, the graphene dendritic structure on the surface of the graphene-metal composite coating is more easily deplated into the ionic liquid due to the tip effect. After the graphene dendritic structure is deplated, the surface of the graphene-metal composite material coating is smoother, the graphene-metal composite material coating formed in the next pulse period is combined with a substrate more compactly, and finally a high-quality graphene-metal composite material coating is formed. In addition, after the electrodeposition in the positive pulse period, the concentrations of the metal ions and the graphene oxide in the ionic liquid near the cathode substrate are lower than those of the metal ions and the graphene oxide in the whole ionic liquid, so that the concentrations of the metal ions and the graphene oxide in the ionic liquid can be recovered and balanced in the pause period, and the electrodeposition can be continued. Because of the capacitance and resistance values included in the electrodeposition system, the current and voltage have periods of opposite positive and negative values during the pulse, such as when the current has turned from a negative value to a positive value and immediately back to a negative value, and the voltage has not had time to turn from a negative value to a positive value and the current has already turned back to a negative value, both will have periods of opposite positive and negative values, which also function as the above-mentioned rest periods.
Preferably, the ionic liquid is a choline chloride and ethylene glycol system, and the molar ratio of the choline chloride to the ethylene glycol is 1-4: 2; or the ionic liquid is a choline chloride and urea system, and the molar ratio of the choline chloride to the urea is 1-4: 2.
Preferably, the ionic liquid is a choline chloride and ethylene glycol system, and the molar ratio of the choline chloride to the ethylene glycol is 1: 2.
Preferably, the metal ions contained in the ionic liquid are any one or more of copper ions, chromium ions, gallium ions, indium ions, iron ions, nickel ions, silver ions, platinum ions, and gold ions.
Preferably, the metal ions contained in the ionic liquid are copper ions, and the concentration of the copper ions in the ionic liquid is 1-60 mM; the concentration of the graphene oxide in the ionic liquid is 0.2-1.0 g/L.
Preferably, the concentration of copper ions in the ionic liquid is 10-20 mM; the concentration of the graphene oxide in the ionic liquid is 0.4-0.6 g/L.
Preferably, the working time of the forward pulse period of the current control pulse is 10 ms-100 ms, and the current density is-5.5 ASD to-0.1 ASD; the working time of the reverse pulse period is 1-50 ms, and the current density is 0.1-1.5 ASD; the pause time is 10 ms-100 ms.
Preferably, the working time of the forward pulse period of the current control pulse is 30 ms-50 ms, and the current density is-3.5 ASD to-1.5 ASD; the working time of the reverse pulse period is 5-20 ms, and the current density is 0.1-1.0 ASD; the dwell time is 50ms to 70 ms.
Preferably, the working time of the forward pulse period of the voltage control pulse is 10 ms-100 ms, and the voltage is-4.5 to-0.1V; the working time of the reverse pulse period is 1-50 ms, and the voltage is 0.1-2.0V; the pause time is 10 ms-100 ms.
Further, the method comprises the step of stirring the ionic liquid by using a stirrer during the pulse electroplating, wherein the stirring speed is 50-200 r/min. Through stirring, the concentration of metal ions and graphene oxide in the ionic liquid is more favorably recovered to be balanced, and the electrodeposition is favorably continued.
Preferably, all or part of the metal ions in the ionic liquid enter the ionic liquid after being oxidized by the anode.
In another aspect, an embodiment of the present invention provides a PCB, where the PCB includes one or more substrate boards and a bottom conductive filament on the surface of the substrate board, where the bottom conductive filament has a graphene-metal composite layer, and the graphene-metal composite layer is formed by electroplating according to any one of the above technical solutions.
Preferably, the metal element in the graphene-metal composite material layer is any one or more of copper, chromium, gallium, indium, iron, nickel, silver, platinum and gold. It should be understood that the above-mentioned metal elements should correspond to metal ions contained in the ionic liquid.
Preferably, the metal element in the graphene-metal composite material layer is copper, and the graphene-metal composite material is a composite material containing graphene in copper.
Preferably, the base of the bottom layer conductive wire is a copper-containing wire.
In another aspect, an embodiment of the present invention further provides a motor, where the motor includes a motor stator, and the motor stator includes the PCB in any one of the above embodiments. Any one of the graphene-containing conductive wires is printed and wound on a PCB to form a brushless motor stator, so that a novel motor is provided.
Compared with the prior art, the invention has the following beneficial effects:
1. the ion liquid electroplating is used for replacing water-based electroplating in the prior art, firstly, graphene oxide is easy to disperse uniformly in the ion liquid, and sufficient graphene oxide can be adsorbed on the surface of the ultrathin metal coating of the cathode substrate due to Van der Waals force; the ion liquid contains no water and is used as electroplating liquid, so that hydrogen evolution reaction in electrodeposition can be avoided, hydrogen embrittlement of the coating can be avoided, and no wastewater is discharged. The ionic liquid almost has no evaporation and volatilization, and the ionic liquid is easy to regenerate and can be recycled, so that the green and environment-friendly production can be really realized.
2. In the reverse pulse period, the graphene dendritic structure on the surface of the graphene-metal composite coating is more easily deplated into the ionic liquid due to the tip effect. After the graphene dendritic structure is deplated, the surface of the graphene-metal composite material coating is smoother, the graphene-metal composite material coating formed in the next pulse period is combined with a substrate more compactly, and finally a high-quality graphene-metal composite material coating is formed. And the pause period is favorable for the recovery and the balance of the ion concentration in the ionic liquid, so that the recovery of the metal ions and the graphene oxide near the cathode substrate is improved.
3. Compared with the powder sintering technology, the method provided by the invention can be applied to the production of large-area graphene composite material coatings or films.
4. Compared with a chemical vapor deposition method, the method provided by the invention has the advantages of low cost, simple process and no need of preparation environments such as high temperature and high vacuum, and the like, so that the large-area industrial production of the graphene composite metal material can be realized.
5. The conductive circuit of the existing PCB is usually formed by etching an inner layer to form a bottom copper circuit and electroplating on a bottom copper substrate to form secondary copper, and finally a copper conductive circuit with proper thickness is formed, so that the light weight of the PCB is restricted due to the large total weight of the copper conductive circuit. Compared with a copper material, the density of the graphene-metal composite material is lower and the conductivity is higher due to the addition of the electroplated graphene-metal composite material to the bottom copper (or other metals) formed by etching the inner layer of the PCB provided by the invention, so that the conductive circuit of the PCB provided by the invention can reduce the metal consumption and still ensure the calibrated current bearing, and overcomes the shortages that the PCB is further lightened and the current bearing is further improved.
6. The graphene-metal composite material has good mechanical property and heat conducting property, compared with the existing PCB, the PCB provided by the invention has the advantages of wear resistance, mechanical damage resistance and heat dissipation, and can avoid the obvious change of the wiring resistance of the conducting circuit due to severe temperature rise during the use period of the PCB or after the PCB is used for a long time, thereby avoiding the influence on the transmission of electric signals.
7. The conductive wire containing graphene is printed and wound on the PCB to form the brushless motor stator which is lighter and thinner and can bear higher current than the brushless motor stator manufactured by winding the conductive wire by using a mold frame or by using other methods.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and it will be apparent to those skilled in the art that other relevant drawings can be obtained from the drawings without inventive effort.
Fig. 1 is a graph showing the change in pulse current density according to the first embodiment of example 1.
Fig. 2 is a graph showing the change of the pulse voltage according to the first embodiment in example 1.
Fig. 3 is a macroscopic view of a graphene-metal composite plating layer prepared in the first embodiment of example 1.
Fig. 4 is a raman spectrum of a graphene-metal composite plating layer prepared in the first embodiment of example 1.
Fig. 5 is a graph showing the change in the pulse current density according to the second embodiment in example 1.
Fig. 6 is a graph showing the change of the pulse voltage according to the second embodiment in example 1.
Fig. 7 is a raman spectrum of a graphene-metal composite plating layer prepared in the second embodiment of example 1.
Fig. 8 is a graph showing the change in the pulse current density according to the third embodiment in example 1.
Fig. 9 is a graph showing the change in pulse voltage according to the third embodiment in example 1.
Fig. 10 is a raman spectrum of a plating layer of a graphene-metal composite material prepared in the third embodiment of example 1.
Fig. 11 is a raman spectrum of a graphene-metal composite plating layer prepared in the fourth embodiment of example 1.
Fig. 12 is a raman spectrum of a graphene-metal composite plating layer prepared in the fifth embodiment of example 1.
Fig. 13 is a schematic structural diagram of a PCB provided in embodiment 2.
The reference numbers in the figures illustrate:
10-a substrate sheet; 20-a bottom layer conductive filament; 30-graphene-metal composite layer.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the invention without inventive step, are within the scope of the invention.
Example 1:
compared with the prior art, such as a water-based electroplating method, a powder sintering method and a chemical vapor deposition method, the method is more green and environment-friendly, can be applied to production of large-area graphene composite coatings or films, and is lower in cost, simple in process, free of preparation environments such as high temperature and high vacuum and the like.
The method specifically comprises the following steps: taking an ionic liquid as an electroplating liquid, wherein graphene oxide is dispersed in the ionic liquid, and the ionic liquid also contains metal ions; depositing a graphene-metal composite material coating on a cathode substrate by a current control pulse, wherein the current control pulse comprises a positive pulse period when current and voltage are negative on a deposition surface, a reverse pulse period when current and voltage are positive on the deposition surface, and a period comprising one or more of the following a-c, a pause period when the current is zero, b period when the current is negative and the voltage is positive, c period when the current is positive and the voltage is negative; or depositing a graphene-metal composite coating on the cathode substrate by a voltage control pulse, wherein the voltage control pulse comprises a positive pulse period when the voltage and the current are negative on the deposition surface, a reverse pulse period when the voltage and the current are positive on the deposition surface, and a period comprising one or more of d-f, a pause period when the d voltage is zero, a period when the e voltage is negative and the current is positive, and a period when the f voltage is positive and the current is negative.
Based on the above-described method, this example lists the following five embodiments, and attaches the experimental results of each embodiment.
The first embodiment is as follows:
the ionic liquid system is a choline chloride and ethylene glycol system, and the molar ratio of the choline chloride to the ethylene glycol is 1: 2. The metal ions contained in the ionic liquid were copper ions, and the concentration of copper ions was 15 mM. The concentration of the graphene oxide in the ionic liquid is 0.5 g/L.
And depositing on a cathode substrate (copper sheet) by using current control pulses to obtain the graphene-metal composite material coating. Wherein, the working time of the positive pulse period in each complex waveform pulse is 40ms, and the current density is-2.5 ASD; the working time of the reverse pulse period is 10ms, and the current density is 0.5 ASD; the dwell time is 60 ms. The pulse current density and the corresponding voltage variation are shown in fig. 1 and 2.
During the complex pulse electroplating, the ionic liquid is stirred by a stirrer, so that the graphene oxide concentration and the copper ion concentration between the cathode and the anode can be rapidly recovered to be balanced, and the stirring speed of the stirrer is 100 r/min.
Referring to fig. 3, a graphene-metal composite plating layer is deposited on the cathode substrate (copper sheet). Referring to fig. 4, in a raman spectrum of the graphene-metal composite plating layer prepared according to the present embodiment, 1580cm-1The near part has an obvious characteristic peak G peak, 2700cm-1The near has a distinct characteristic peak G' peak, 1270-1450cm-1And the graphene-metal composite material coating in the graph 3 can be characterized to contain graphene according to the characteristics of the Raman spectrogram.
The second embodiment is as follows:
the ionic liquid system is a choline chloride and ethylene glycol system, and the molar ratio of the choline chloride to the ethylene glycol is 1: 2. The metal ions contained in the ionic liquid were copper ions, and the concentration of copper ions was 20 mM. The concentration of the graphene oxide in the ionic liquid is 0.6 g/L.
And depositing the current control pulse on a cathode substrate (a stainless steel sheet) to obtain the graphene-metal composite material coating. Wherein, the working time of the positive pulse period in each complex waveform pulse is 40ms, and the current density is-3.5 ASD; the working time of the reverse pulse period is 15ms, and the current density is 1.0 ASD; the dwell time is 60 ms. The pulse current density and the corresponding voltage variation are shown in fig. 5 and 6.
During the complex pulse electroplating, the ionic liquid is stirred by a stirrer, so that the graphene oxide concentration and the copper ion concentration between the cathode and the anode can be rapidly recovered to be balanced, and the stirring speed of the stirrer is 150 r/min.
Referring to fig. 7, in a raman spectrum of the graphene-metal composite plating layer prepared according to the present embodiment, 1580cm-1The near part has an obvious characteristic peak G peak, 2700cm-1The near has a more obvious characteristic peak G' peak, 1270--1And a characteristic peak D is obvious nearby to characterize the graphene.
The third concrete implementation mode:
the ionic liquid system is a choline chloride and ethylene glycol system, and the molar ratio of the choline chloride to the ethylene glycol is 1: 1. The metal ions contained in the ionic liquid were copper ions, and the concentration of copper ions was 5 mM. The concentration of the graphene oxide in the ionic liquid is 0.2 g/L.
And depositing on a cathode substrate (copper sheet) by using current control pulses to obtain the graphene-metal composite material coating. Wherein, the working time of the positive pulse period in each complex waveform pulse is 40ms, and the current density is-1.5 ASD; the working time of the reverse pulse period is 5ms, and the current density is 1.0 ASD; the dwell time is 60 ms. The pulse current density and the corresponding voltage variation are shown in fig. 8 and 9.
Referring to fig. 10, in a raman spectrum of the graphene-metal composite plating layer prepared according to the present embodiment, 1580cm-1Has a more obvious characteristic peak G peak near 2700cm-1The near has a more obvious characteristic peak G' peak, 1270--1And a characteristic peak D is obvious nearby to characterize the graphene.
The fourth concrete implementation mode:
the ionic liquid system is a choline chloride and ethylene glycol system, and the molar ratio of the choline chloride to the ethylene glycol is 2: 1. The metal ions contained in the ionic liquid were copper ions, and the concentration of copper ions was 60 mM. The concentration of the graphene oxide in the ionic liquid is 1.0 g/L.
And depositing on a cathode substrate (copper sheet) by using current control pulses to obtain the graphene-metal composite material coating. Wherein, the working time of the positive pulse period in each complex waveform pulse is 10ms, and the current density is-1.5 ASD; the working time of the reverse pulse period is 5ms, and the current density is 1.5 ASD; the dwell time is 10 ms.
During the complex pulse electroplating, the ionic liquid is stirred by a stirrer, so that the graphene oxide concentration and the copper ion concentration between the cathode and the anode can be quickly recovered to be balanced, and the stirring speed of the stirrer is 200 r/min.
Referring to fig. 11, in a raman spectrum of the graphene-metal composite plating layer prepared according to the present embodiment, 1580cm-1Has a more obvious characteristic peak G peak near 2700cm-1The near has a more obvious characteristic peak G' peak, 1270--1And a characteristic peak D is obvious nearby to characterize the graphene.
The fifth concrete implementation mode:
the ionic liquid system is a choline chloride and urea system, and the molar ratio of the choline chloride to the urea is 1: 2. The metal ions contained in the ionic liquid were copper ions, and the concentration of copper ions was 60 mM. The concentration of the graphene oxide in the ionic liquid is 1.0 g/L.
And depositing the voltage control pulse on a cathode substrate (copper sheet) to obtain the graphene-metal composite material coating. Wherein, the working time of the positive pulse period in each complex waveform pulse is 80ms, and the voltage is-3.0V; the working time of the reverse pulse period is 30ms, and the voltage is 1.0V; the dwell time is 80 ms.
During the complex pulse electroplating, the ionic liquid is stirred by a stirrer, so that the graphene oxide concentration and the copper ion concentration between the cathode and the anode can be quickly recovered to be balanced, and the stirring speed of the stirrer is 50 r/min.
Referring to fig. 12, in a raman spectrum of the graphene-metal composite plating layer prepared according to the present embodiment, 1580cm-1The near part has an obvious characteristic peak G peak, 2700cm-1The near has a more obvious characteristic peak G' peak, 1270--1And a characteristic peak D is obvious nearby to characterize the graphene.
According to the above embodiments, the inventors found that when the pulse is controlled by the current, the working time of the forward pulse is controlled to 10 to 100ms, and the current density is controlled to-3.5 to-1.5 ASD; controlling the working time of reverse pulse to be 5-20 ms and controlling the current density to be 0.1-1.0 ASD; controlling the pause time to be 50-70 ms; the ionic liquid is a choline chloride and ethylene glycol system, wherein the molar ratio of the choline chloride to the ethylene glycol is 1: 2; the concentration of graphene oxide in the ionic liquid is 0.4-0.6 g/L, and the concentration of copper ions is 10-20 mM; stirring the ionic liquid by using a stirrer during the electroplating period, wherein the stirring speed is controlled to be 50-200 r/min; can prepare a graphene-metal composite material coating with higher quality.
In the five embodiments described above, the copper ions are derived from CuCl 2. But not limited thereto, the copper ions may also be derived from copper-containing sulfate, acetate, bromide, fluoride, iodide, hydroxide, nitride, oxalate, citrate, phosphate, tungstate, hydrate, or combinations thereof. Or the anode of the electrodeposition system is copper, so that part or all of the copper ions in the ionic liquid can originate from the oxidation of the anode.
It should be understood that, in the five embodiments, copper ions are selected as the metal ions in the ionic liquid, because the graphene-copper composite material coating is prepared. Based on the five embodiments, the copper ions can be simply replaced by chromium ions, gallium ions, indium ions, iron ions, nickel ions, silver ions, platinum ions or gold ions, or the metal ions include any two or more of the above ions, so that a composite plating layer of graphene and other metals or alloys can be prepared. The graphene-metal composite material coating is specifically formed by dispersing graphene in a metal body or an alloy body.
In the pause period, the graphene oxide is adsorbed on the surface of the cathode substrate by van der waals force, and although the complex pulse in the above embodiments includes the pause period, the same effect is achieved in the pause period when the current is negative and the voltage is positive, or when the current is positive and the voltage is negative, and therefore, the pause period can be replaced by a period when the current is negative and the voltage is positive, or a period when the current is positive and the voltage is negative.
Example 2:
referring to fig. 13, the present embodiment provides a PCB, which includes one or more layers of a substrate board 10 and a bottom conductive wire 20 on a surface of the substrate board 10, wherein the bottom conductive wire 20 is covered with a graphene-metal composite layer 30, and the graphene-metal composite layer 30 is formed by electroplating according to the method provided in embodiment 1.
When the PCB is manufactured, firstly, a substrate plate 10 can be manufactured by utilizing the prior art, and the surface of the substrate plate 10 is covered with metal foil; etching the metal foil into a bottom layer conductive wire 20 according to the design result of the PCB conductive circuit; finally, according to the method provided in example 1, the graphene-metal composite plating layer is formed by electroplating using the bottom conductive wire 20 as a cathode substrate.
For example, the metal ions contained in the ionic liquid may be copper ions, chromium ions, gallium ions, indium ions, iron ions, nickel ions, silver ions, platinum ions, or gold ions, or the metal ions may include any two or more of the foregoing ions. Correspondingly, the metal element in the graphene-metal composite material plating layer on the surface of the bottom conductive wire 20 is copper, chromium, gallium, indium, iron, nickel, silver, platinum or gold, or the metal element includes any two or more of the above elements.
For example, the metal ions contained in the ionic liquid are copper ions, and correspondingly, the metal element in the graphene-metal composite material plating layer on the surface of the bottom conductive wire 20 is copper. The graphene-metal composite material is formed by dispersing graphene in a copper matrix.
For example, the metal foil coated on the substrate board 10 may be a copper foil, which is etched into the bottom conductive wires 20, and the bottom conductive wires 20 are copper wires. It should be understood that the underlying conductive wire 20 may also have a variety of other options, such as a silver wire, a gold wire, a platinum wire, and so forth.
The PCB may also be applied to a motor, for example, the present embodiment further provides a motor, where the motor includes a motor stator, and the motor stator is a brushless motor stator formed by printing graphene-containing conductive wires on the PCB.
The above description is only an embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of changes or substitutions within the technical scope of the present invention, and the present invention should be covered by the scope of the present invention.
Claims (16)
1. A method for electroplating a graphene-metal composite coating by using complex pulses is characterized by comprising the following steps:
taking an ionic liquid as an electroplating liquid, wherein graphene oxide is dispersed in the ionic liquid, and the ionic liquid also contains metal ions;
depositing a graphene-metal composite material coating on a cathode substrate by a current control pulse, wherein the current control pulse comprises a positive pulse period when current and voltage are negative on a deposition surface, a reverse pulse period when current and voltage are positive on the deposition surface, and a period comprising one or more of the following a-c, a pause period when the current is zero, b period when the current is negative and the voltage is positive, c period when the current is positive and the voltage is negative; alternatively, the first and second electrodes may be,
and depositing a graphene-metal composite coating on the cathode substrate by a voltage control pulse, wherein the voltage control pulse comprises a positive pulse period when the voltage and the current are negative on the deposition surface, a reverse pulse period when the voltage and the current are positive on the deposition surface, and a period comprising one or more of d-f, a pause period when the d voltage is zero, a period when the e voltage is negative and the current is positive, and a period when the f voltage is positive and the current is negative.
2. The method according to claim 1, wherein the ionic liquid is a choline chloride and ethylene glycol system, and the molar ratio of the choline chloride to the ethylene glycol is 1-4: 2; or the ionic liquid is a choline chloride and urea system, and the molar ratio of the choline chloride to the urea is 1-4: 2.
3. The method according to claim 2, wherein the ionic liquid is a choline chloride and ethylene glycol system, and the molar ratio of the choline chloride to the ethylene glycol is 1: 2.
4. The method according to claim 1, wherein the metal ions contained in the ionic liquid are any one or more of copper ions, chromium ions, gallium ions, indium ions, iron ions, nickel ions, silver ions, platinum ions, and gold ions.
5. The method according to claim 4, wherein the metal ions contained in the ionic liquid are copper ions, and the concentration of the copper ions in the ionic liquid is 1-60 mM; the concentration of the graphene oxide in the ionic liquid is 0.2-1.0 g/L.
6. The method according to claim 5, wherein the concentration of copper ions in the ionic liquid is 10 to 20 mM; the concentration of the graphene oxide in the ionic liquid is 0.4-0.6 g/L.
7. The method according to claim 1, wherein the current control pulse has a forward pulse period of 10ms to 100ms on time, a current density of-5.5 ASD to-0.1 ASD; the working time of the reverse pulse period is 1-50 ms, and the current density is 0.1-1.5 ASD; the pause time is 10 ms-100 ms.
8. The method according to claim 7, wherein the current control pulse has a forward pulse period of 30ms to 50ms on time, a current density of-3.5 to-1.5 ASD; the working time of the reverse pulse period is 5-20 ms, and the current density is 0.1-1.0 ASD; the dwell time is 50ms to 70 ms.
9. The method according to claim 1, wherein the working time of the positive pulse period of the voltage control pulse is 10ms to 100ms, the voltage is-4.5 to-0.1V; the working time of the reverse pulse period is 1-50 ms, and the voltage is 0.1-2.0V; the pause time is 10 ms-100 ms.
10. The method according to claim 1, further comprising stirring the ionic liquid with a stirrer at a speed of 50 to 200r/min during the pulse plating.
11. The method of claim 1, wherein all or a portion of the metal ions in the ionic liquid are introduced into the ionic liquid by anodic oxidation.
12. A PCB comprising one or more substrate sheets and a bottom conductive filament on a surface of the substrate sheets, the bottom conductive filament having a graphene-metal composite layer electroplated by the method of any of claims 1-11.
13. The PCB of claim 12, wherein the metal element in the graphene-metal composite layer is any one or more of copper, chromium, gallium, indium, iron, nickel, silver, platinum, and gold.
14. The PCB of claim 13, wherein the metal element in the graphene-metal composite layer is copper, and the graphene-metal composite is a copper-graphene-in-copper composite.
15. The PCB of claim 14, wherein a base of the bottom layer conductive wire is a copper-containing wire.
16. An electrical machine comprising a machine stator, wherein the machine stator comprises a PCB as claimed in any one of claims 12 to 15.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810646051.XA CN110636693A (en) | 2018-06-21 | 2018-06-21 | Method for electroplating graphene-metal composite material coating by using complex pulse, PCB and motor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810646051.XA CN110636693A (en) | 2018-06-21 | 2018-06-21 | Method for electroplating graphene-metal composite material coating by using complex pulse, PCB and motor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110636693A true CN110636693A (en) | 2019-12-31 |
Family
ID=68966681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810646051.XA Pending CN110636693A (en) | 2018-06-21 | 2018-06-21 | Method for electroplating graphene-metal composite material coating by using complex pulse, PCB and motor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110636693A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109628983A (en) * | 2019-02-26 | 2019-04-16 | 西南大学 | A kind of preparation method of metal-graphite alkene composite-plated material |
| CN111864063A (en) * | 2020-07-09 | 2020-10-30 | 复旦大学 | Three-dimensional capacitor preparation method |
| CN111943175A (en) * | 2020-07-29 | 2020-11-17 | 北海惠科光电技术有限公司 | Graphene film, manufacturing method of graphene material and display panel |
-
2018
- 2018-06-21 CN CN201810646051.XA patent/CN110636693A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109628983A (en) * | 2019-02-26 | 2019-04-16 | 西南大学 | A kind of preparation method of metal-graphite alkene composite-plated material |
| CN111864063A (en) * | 2020-07-09 | 2020-10-30 | 复旦大学 | Three-dimensional capacitor preparation method |
| CN111943175A (en) * | 2020-07-29 | 2020-11-17 | 北海惠科光电技术有限公司 | Graphene film, manufacturing method of graphene material and display panel |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5466664B2 (en) | Porous metal foil and method for producing the same | |
| JP5400826B2 (en) | Composite metal foil and manufacturing method thereof | |
| EP3202957B1 (en) | Aluminum plate | |
| CN110636693A (en) | Method for electroplating graphene-metal composite material coating by using complex pulse, PCB and motor | |
| JP5920541B1 (en) | Silver coated copper powder and conductive paste, conductive paint, conductive sheet using the same | |
| JP4878452B2 (en) | Composite coated copper wire and composite coated enameled copper wire | |
| MX2013010443A (en) | Sheet assembly with aluminum based electrodes. | |
| CN105112958A (en) | Method for obtaining nano-porous silver in base-material-loaded dealloying mode | |
| CN102133636B (en) | Method for preparing anti-migration flaky silver coated copper powder | |
| CN110029382A (en) | A kind of process of surface treatment and its related directly electroplating technology for being directly electroplated | |
| CN107419315A (en) | A kind of preparation method of magnesium alloy black micro-arc oxidation films | |
| JP2022120813A (en) | Ultrathin copper foil, and method of producing the same | |
| JP6698059B2 (en) | Method for preparing high conductivity base metal thick film conductor paste | |
| TW201337990A (en) | Method for manufacturing electrode material for aluminum electrolytic capacitor | |
| CN102548202B (en) | Roughly-processed copper foil and manufacture method thereof | |
| TWI482878B (en) | Acidic electroless copper plating system and copper plating method using the same | |
| CN114059116B (en) | Method for preparing FeCoNiCuSn high-entropy alloy through electrodeposition | |
| TW201224161A (en) | Method for producing aluminum structure and aluminum structure | |
| JP4948656B2 (en) | Perforated roughening copper foil for secondary battery current collector, method for producing the same, and negative electrode for lithium ion secondary battery | |
| JP5199892B2 (en) | Electrolytic oxidation treatment method and electrolytic oxidation treatment metal material | |
| JP5735265B2 (en) | Method for producing porous metal body having high corrosion resistance | |
| CN110629272A (en) | Method for preparing graphene composite material coating | |
| CN112458518A (en) | Preparation method of high-conductivity copper-based composite material | |
| CN110172713A (en) | A kind of tin plating copper foil processing method of high shielding properties | |
| JP2003231990A (en) | Electroplating method by using thin-film-shaped particle having frame consisting of carbon |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20230913 Address after: Room 101, 201, 301, 401, 2nd Floor, Building 10, Shengyue Garden, No. 33 Shunye East Road, Xingtan Town, Shunde District, Foshan City, Guangdong Province, 528305 (Residence application) Applicant after: Foshan qiaoluan Technology Co.,Ltd. Address before: 629000 Electronic Testing Center, 1st and 6th floors, Yulong Road, Economic and Technological Development Zone, Suining City, Sichuan Province Applicant before: SICHUAN JUCHUANG SHIMOXI TECHNOLOGY Co.,Ltd. Applicant before: Huang Yingchun |
|
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240104 Address after: Room 03, Shared Office Area, 2nd Floor, Building 22, No. 1889 Huandao East Road, Hengqin New District, Zhuhai City, Guangdong Province, 529031 Applicant after: Yaoling (Guangdong) New Energy Technology Co.,Ltd. Address before: Room 101, 201, 301, 401, 2nd Floor, Building 10, Shengyue Garden, No. 33 Shunye East Road, Xingtan Town, Shunde District, Foshan City, Guangdong Province, 528305 (Residence application) Applicant before: Foshan qiaoluan Technology Co.,Ltd. |
|
| TA01 | Transfer of patent application right |