WO2017206645A1 - 导电粒子及其制造方法以及导电胶及其制造方法 - Google Patents

导电粒子及其制造方法以及导电胶及其制造方法 Download PDF

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WO2017206645A1
WO2017206645A1 PCT/CN2017/082422 CN2017082422W WO2017206645A1 WO 2017206645 A1 WO2017206645 A1 WO 2017206645A1 CN 2017082422 W CN2017082422 W CN 2017082422W WO 2017206645 A1 WO2017206645 A1 WO 2017206645A1
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layer
conductive
graphene
metal layer
microspheres
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PCT/CN2017/082422
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English (en)
French (fr)
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胡海峰
谢涛峰
曾亭
颜亮
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京东方科技集团股份有限公司
合肥鑫晟光电科技有限公司
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Priority to US15/577,205 priority Critical patent/US11084956B2/en
Publication of WO2017206645A1 publication Critical patent/WO2017206645A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0036—Details
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

  • Embodiments of the present disclosure relate to conductive particles, a method of manufacturing the same, and a conductive paste including the conductive particles and a method of manufacturing the same.
  • the conductive paste mainly contains conductive particles and an insulating rubber material. Conductive particles are the key components in the conductive paste that act as a conductive function. There are two main types of conductive particles: metal powder, and polymer microspheres coated with metal.
  • the problem of crushing strength may cause cracking of conductive particles, resulting in problems such as product scratching and malfunction.
  • the conductive paste is an anisotropic conductive film, it also causes a problem of losing the anisotropic conduction function. To this end, it is necessary to rework the conductive particles.
  • the success rate of conductive particle repair is not very high, which leads to an increase in the number of working hours per unit product, affecting product yield and increasing the cost per unit of product.
  • Embodiments of the present disclosure provide a novel conductive particle, a method of manufacturing the same, and a conductive paste including the conductive particle, and a method of manufacturing the same, which can maintain the conductive function of the conductive particle while improving the withstand voltage of the conductive particle.
  • the structure of the new conductive particles ensures the use of conductive adhesives over a wider range of pressures, making the conductive adhesives more versatile. Moreover, it can reduce the time consumption per unit of product, reduce costs, and increase production capacity.
  • a conductive particle comprising:
  • a 3D graphene layer and a metal layer covering the conductive polymer layer are described.
  • the surface of the core microspheres of the conductive particles is coated with a conductive polymer layer and the surface of the conductive polymer layer is coated with a 3D graphene layer and a metal layer. Since the 3D graphene layer has extremely high pressure resistance and the conductive polymer layer has high conductivity, the anisotropic conductive function of the conductive particles can be maintained while increasing the withstand voltage of the conductive particles. Thereby, it is ensured that the conductive paste is used over a wider pressure range, and the time consumption per unit product is reduced, the cost is reduced, and the productivity is increased.
  • the 3D graphene layer coats the conductive polymer layer
  • the metal layer coats the 3D graphene layer.
  • the surface of the core microsphere by coating the surface of the core microsphere with the conductive polymer layer, the surface of the conductive polymer layer is covered with the 3D graphene layer, and the surface of the 3D graphene layer is covered with the metal layer, that is,
  • the addition of the conductive polymer layer and the 3D graphene layer between the core microspheres and the metal layer can improve the conductive strength of the conductive particles while maintaining the conductive function of the conductive particles, thereby ensuring the use of the conductive paste over a wider pressure range.
  • the metal layer covers the conductive polymer layer
  • the 3D graphene layer covers the metal layer.
  • the surface of the core microsphere by coating the surface of the core microsphere with the conductive polymer layer, the surface of the conductive polymer layer is covered with the metal layer, and the surface of the metal layer is covered with the 3D graphene layer, which can improve the conductivity.
  • the compressive strength of the particles while maintaining the conductive function of the conductive particles ensures that the conductive paste is used over a wider range of pressures.
  • the core microspheres are monodisperse polystyrene microspheres.
  • the polystyrene since the polystyrene has a light weight and a controllable particle size, the conductive particles and the conductive paste thus produced also have the advantages of light weight and controllable particle size.
  • polystyrene microspheres are readily available and can reduce product costs.
  • the conductive polymer layer is a polyaniline layer. Root According to this exemplary embodiment, since polyaniline has high conductivity and is simple in synthesis, the finally formed conductive particles can maintain a high conductive function even under high extrusion lightness, and can reduce production cost.
  • the metal layer is a gold layer.
  • gold is used as the material of the metal layer, and the conductive property of the conductive particles can be ensured even if the thickness of the gold layer is small.
  • the core microspheres have an average diameter of 0.1 ⁇ m to 10 ⁇ m. According to this exemplary embodiment, by using the core microspheres having an average diameter falling within the range to fabricate the conductive particles and the conductive paste, the conductivity of the formed conductive particles and the conductive paste can be made better, and the core micro can be avoided. The agglomeration of the balls causes the conductive polymer layer to completely encapsulate the core microspheres.
  • a method of manufacturing conductive particles comprising:
  • the surface of the composite microspheres is coated with a 3D graphene layer and a metal layer.
  • the surface of the core microspheres of the conductive particles is coated with a conductive polymer layer and the surface of the conductive polymer layer is coated with a 3D graphene layer and a metal layer. Since the 3D graphene layer has extremely high pressure resistance and the conductive polymer layer has high conductivity, it is possible to maintain the conductive strength of the conductive particles while maintaining the conductive function of the conductive particles. Thereby, it is ensured that the conductive paste is used over a wider pressure range, and the time consumption per unit product is reduced, the cost is reduced, and the productivity is increased.
  • the coating the surface of the core microsphere with the conductive polymer layer includes the following steps:
  • the conductive monomer is polymerized on the surface of the core microsphere via an initiator to form a conductive polymer layer.
  • a polymer layer having high electrical conductivity can be formed simply and efficiently on the surface of the core microspheres.
  • the finally formed conductive particles can maintain a high conductive function even under high extrusion strength, and the production cost can be reduced.
  • the coating the surface of the composite microsphere with a 3D graphene layer and a metal layer includes:
  • the surface of the 3D graphene layer is coated with the metal layer.
  • the surface of the core microsphere by coating the surface of the core microsphere with the conductive polymer layer, the surface of the conductive polymer layer is covered with the 3D graphene layer, and the surface of the 3D graphene layer is covered with the metal layer, that is,
  • the addition of the conductive polymer layer and the 3D graphene layer between the core microspheres and the metal layer can improve the conductive strength of the conductive particles while maintaining the conductive function of the conductive particles, thereby ensuring the use of the conductive paste over a wider pressure range.
  • the coating the surface of the composite microsphere with the 3D graphene layer includes:
  • the 3D graphene powder is dispersed, and the composite microspheres are added to the dispersed 3D graphene powder to obtain a composite microsphere coated with a 3D graphene layer.
  • the cost of the conductive particles can be reduced by conveniently and easily forming a 3D graphene layer by using a mature micromachining process.
  • the surface of the 3D graphene layer coated with a metal layer includes:
  • the composite microsphere coated with the 3D graphene layer is placed in a metal layer forming solution, and a metal layer is formed on the surface of the composite microsphere coated by the 3D graphene layer by electrochemical action, thereby obtaining the conductive layer. particle.
  • the electrical conductivity of the conductive particles can be improved by forming a metal layer on the surface of the composite microspheres coated with the 3D graphene layer.
  • the coating the surface of the composite microsphere with a 3D graphene layer and a metal layer includes:
  • the surface of the conductive polymer layer is covered with the metal layer, and the surface of the metal layer is covered with the 3D graphene layer, which can improve the conductivity.
  • the compressive strength of the particles while maintaining the conductive function of the conductive particles ensures that the conductive paste is used over a wider range of pressures.
  • the coating the surface of the composite microsphere with the metal layer includes:
  • the composite microspheres are placed in a metal layer forming solution, and a metal layer is formed on the surface of the composite microspheres by electrochemical action, thereby obtaining composite microspheres coated with the metal layer.
  • the electrical conductivity of the conductive particles can be improved by forming a metal layer on the surface of the composite microspheres.
  • the surface of the metal layer coated with the 3D graphene layer includes:
  • the 3D graphene powder is dispersed, and the metal microlayer-coated composite microspheres are added to the dispersed 3D graphene powder to obtain the conductive particles.
  • the cost of the conductive particles can be reduced by conveniently and easily forming a 3D graphene layer by using a mature micromachining process.
  • the core microspheres are monodisperse polystyrene microspheres.
  • the polystyrene since the polystyrene has a light weight and a controllable particle size, the conductive particles and the conductive paste thus produced also have the advantages of light weight and controllable particle size.
  • polystyrene microspheres are readily available and can reduce product costs.
  • the conductive polymer layer is a polyaniline layer.
  • polyaniline since polyaniline has high conductivity and is simple in synthesis, the finally formed conductive particles can maintain a high conductive function even under high extrusion lightness, and can reduce production cost.
  • the metal layer is a gold layer.
  • gold is used as the material of the metal layer, and even if the thickness of the gold layer is small, it is ensured Conductive properties of conductive particles.
  • the core microspheres have an average diameter of 0.1 ⁇ m to 10 ⁇ m. According to this exemplary embodiment, by using the core microspheres having an average diameter falling within the range to fabricate the conductive particles and the conductive paste, the conductivity of the formed conductive particles and the conductive paste can be made better, and the core micro can be avoided. The agglomeration of the balls causes the conductive polymer layer to completely encapsulate the core microspheres.
  • the surfactant is an amphoteric coupling agent including, but not limited to, a chromium complex coupling agent, a silane coupling agent, a titanate coupling agent, a zirconium-containing coupling agent.
  • a conductive paste comprising the conductive particles according to the first aspect.
  • the conductive particles of the first aspect are included and the conductive particles can maintain their conductive function while increasing their withstand voltage, the conductive paste can be used over a wider pressure range, and the cost can be reduced and improved. Capacity.
  • a method of producing a conductive paste comprising the step of uniformly distributing the conductive particles of the first aspect in an insulating rubber.
  • the conductive paste is prepared by uniformly distributing the conductive particles of the first aspect in an insulating rubber. Since the conductive particles therein maintain their conductive function while increasing their withstand voltage, it is possible to provide a conductive paste which can be used over a wider pressure range, and it is possible to reduce cost and increase productivity.
  • the embodiment of the present disclosure forms a conductive polymer layer on the surface of the core microsphere and coats the surface of the conductive polymer layer with a 3D graphene layer and a metal layer to form conductive particles, and further adopts the conductive polymer layer.
  • the conductive particles form a conductive paste. Since the 3D graphene layer has extremely high pressure resistance and the conductive polymer layer has high conductivity, it is possible to maintain the conductive strength of the conductive particles while maintaining the conductive function of the conductive particles. Thereby, it is ensured that the conductive paste is used over a wider pressure range, and the time consumption per unit product is reduced, the cost is reduced, and the productivity is increased.
  • FIG. 1A is a cross-sectional view of conductive particles in accordance with an exemplary embodiment of the present disclosure
  • FIG. 1B is a cross-sectional view of conductive particles in accordance with another exemplary embodiment of the present disclosure.
  • FIG. 2A is a flow diagram of fabricating the conductive particles illustrated in FIG. 1A in accordance with an exemplary embodiment of the present disclosure
  • FIG. 2B is a flow diagram of fabricating the conductive particles illustrated in FIG. 1B in accordance with another exemplary embodiment of the present disclosure.
  • a novel conductive particle includes core microspheres, a conductive polymer layer covering the core microspheres, and a 3D graphene layer and a metal layer covering the conductive polymer layer.
  • FIG. 1A is a cross-sectional view of conductive particles in accordance with an exemplary embodiment of the present disclosure.
  • the conductive particles include a core microsphere 10, a conductive polymer layer 12 covering the core microspheres 10, a 3D graphene layer 14 covering the conductive polymer layer 12, and a 3D graphene coating layer.
  • FIG. 1B is a cross-sectional view of conductive particles in accordance with another exemplary embodiment of the present disclosure.
  • the conductive particles include a core microsphere 10, a conductive polymer layer 12 covering the core microspheres 10, a metal layer 16 covering the conductive polymer layer 12, and a 3D covering the metal layer 16.
  • a micron or nano microsphere such as a polymer material of polyvinyl chloride, polystyrene or the like or an inorganic material such as SiO 2 , TiO 2 or the like can be used.
  • monodisperse polystyrene microspheres are preferably used. Due to the light weight and controllable particle size of the polystyrene, the conductive particles and the conductive paste thus produced have the advantages of light weight and controllable particle size. Moreover, polystyrene microspheres are readily available and can reduce product cost.
  • the diameter of the core microspheres 10 There is no particular limitation on the diameter of the core microspheres 10.
  • the conductivity of the conductive paste depends on the conductivity of the conductive particles. Under the premise of ensuring conductive conduction, the smaller the particle size of the conductive particles, the better the conductivity of the formed conductive paste.
  • the core microspheres 10 which form the base structure of the conductive particles have an average diameter of 10 ⁇ m or less.
  • the core microspheres 10 is too small, agglomeration of the core microballoons 10 may occur. In order to avoid agglomeration of the core microballoons 10 so that the conductive polymer layer 12 completely encapsulates the core microspheres 10, it is preferred that the core microspheres have an average diameter of 0.1 ⁇ m or more.
  • a conductive polymer material such as polypyrrole, polyparaphenylene, polyphenylene sulfide, polyaniline or the like can be used.
  • polyaniline is preferably used as the material of the conductive polymer layer 12 because of simple synthesis, low cost, and high electrical conductivity.
  • the thickness of the conductive polymer layer 12 may have a thickness of 100 to 500 nm.
  • the thickness of the 3D graphene layer 14 may have a thickness of 50 to 200 nm.
  • a metal material such as gold, silver, copper or the like or an alloy material thereof can be used.
  • gold is used as the material of the metal layer 16, and the electrical conductivity of the conductive particles can be ensured even if the thickness of the gold layer is small.
  • the thickness of the metal layer 16 may have a thickness of 10 to 100 nm.
  • a method of manufacturing conductive particles includes:
  • the surface of the composite microspheres is coated with a 3D graphene layer and a metal layer.
  • the coating the surface of the composite microsphere with a 3D graphene layer and a metal layer comprises coating the surface of the composite microsphere with the 3D graphene layer and using the gold The genus layer coats the surface of the 3D graphene layer to obtain the conductive particles shown in FIG. 1A.
  • the coating the surface of the composite microsphere with a 3D graphene layer and a metal layer comprises coating the surface of the composite microsphere with the metal layer and using the 3D graphene layer The surface of the metal layer is coated to obtain conductive particles as shown in FIG. 1B.
  • FIG. 2A is a flow diagram of fabricating the conductive particles illustrated in FIG. 1A, in accordance with an exemplary embodiment of the present disclosure.
  • step S210 the surface of the core microspheres 10 is covered with a conductive polymer layer 12.
  • the step may specifically include: treating the core microspheres 10 with a surfactant, and polymerizing the conductive monomers onto the surface of the core microspheres via the initiator to form the conductive polymer layer 12, thereby obtaining composite microspheres.
  • the surfactant may be an amphoteric coupling agent including, but not limited to, a chromium complex coupling agent, a silane coupling agent, a titanate coupling agent, a zirconium-containing coupling agent, and the like.
  • step S212 the surface of the composite microspheres is coated with the 3D graphene layer 14.
  • the step may specifically include: coating the surface of the porous SiO 2 with a graphene layer, followed by HF wet etching to obtain a 3D graphene powder; and uniformly dispersing the 3D graphene powder through the dispersion, and after dispersing The composite microspheres are added to the 3D graphene powder to obtain composite microspheres coated with the 3D graphene layer 14.
  • step S214 the surface of the 3D graphene layer 14 is covered with the metal layer 16.
  • the step may specifically include: placing the composite microsphere coated by the 3D graphene layer 14 in a metal layer forming solution, and electrochemically forming a metal on the surface of the composite microsphere coated by the 3D graphene layer 14. Layer 16 is obtained to obtain the conductive particles of this embodiment.
  • FIG. 2B is a schematic diagram of a flow of manufacturing the conductive particles illustrated in FIG. 1B in accordance with another exemplary embodiment of the present disclosure.
  • step S220 the surface of the core microspheres 10 is covered with the conductive polymer layer 12.
  • the step may specifically include: treating the core microspheres 10 with a surfactant, and polymerizing the conductive monomers on the surface of the core microspheres via an initiator to form the conductive polymer layer 12, thereby obtaining composite microspheres.
  • step S222 the surface of the composite microspheres is covered with a metal layer 16.
  • the The step may specifically include: placing the composite microspheres in a metal layer forming solution, and forming a metal layer 16 on the surface of the composite microspheres by electrochemical action, thereby obtaining composite microspheres coated by the metal layer 16.
  • step S224 the surface of the metal layer 16 is covered with the 3D graphene layer 14.
  • this step may specifically include: surface of the porous SiO 2 coated with the graphene layer, followed by HF wet etching to obtain a graphene 3D powder; and 3D graphene dispersion powder was uniformly dispersed, and after the dispersion The composite microspheres coated with the metal layer 16 were added to the 3D graphene powder to obtain the conductive particles of the present example.
  • a conductive paste including the above-described conductive particles.
  • the type of the conductive adhesive is not specifically limited, and the conductive adhesive may be a homogenous conductive adhesive or a heterogeneous conductive adhesive.
  • a method of manufacturing a conductive paste comprising the step of uniformly distributing the above-mentioned conductive particles in an insulating rubber.
  • the above-mentioned conductive particles can be uniformly distributed in the insulating rubber material in a suitable ratio. According to different requirements and specifications of conductive adhesive, the ratio of conductive particles to insulating rubber can be different.
  • core microspheres monodisperse polystyrene microspheres having an average diameter of 2 ⁇ m were used.
  • the polystyrene microspheres are added to a silane coupling agent (for example, KH-550, etc.) as a surfactant, and reacted for 40 minutes at an oil bath temperature of 140 ° C, and then subjected to centrifugal filtration to obtain a surfactant-treated microsphere.
  • a silane coupling agent for example, KH-550, etc.
  • the above surfactant-treated polystyrene microspheres were magnetically stirred in a hydrochloric acid solution for a while. Then, after the aniline monomer as a conductive monomer is added dropwise and stirred for a while, the aniline monomer is adsorbed on the surface of the polystyrene microspheres. Next, ammonium persulfate and potassium iodate as initiators were added dropwise, so that the aniline monomer was polymerized on the surface of the polystyrene microspheres. After the reaction is completed, a layer of polyaniline conductive layer is formed on the surface of the polystyrene microspheres. By controlling the amount of monomer, The polyaniline conductive layer is controlled at 100-500 nm. Thereby, composite microspheres were obtained.
  • a graphene layer was deposited on the surface of the porous SiO 2 as a template by chemical vapor deposition (CVD) at a temperature of 1,100 ° C, CH 4 , H 2 , and Ar. After cooling to room temperature, the product was immersed in HF liquid for isotropic etching to completely remove the porous SiO 2 template to obtain 3D graphene powder. Then, the 3D graphene powder was dried and annealed at 2250 °C.
  • CVD chemical vapor deposition
  • graphene may be deposited again by CVD using the graphene layer obtained as above as a template, whereby 3D graphene of different thicknesses may be obtained as needed. Different thicknesses of the 3D graphene layer can be obtained by adjusting the conditions according to requirements.
  • the 3D graphene powder may be columnar, spherical, square, or the like depending on the shape of the template such as the porous SiO 2 used.
  • the above 3D graphene powder was added to an aqueous solution of a surfactant (in the present example, a silane coupling agent) as a dispersion to be dispersed.
  • a surfactant in the present example, a silane coupling agent
  • composite microspheres treated with a surfactant on the surface of the polyaniline layer were added to the above dispersion system.
  • the composite microspheres coated with the 3D graphene layer were obtained by centrifugal leaching filtration.
  • a 3D graphene layer of different thickness for example, 50-200 nm
  • the composite microspheres coated with the 3D graphene layer are treated with a surfactant (in this example, a silane coupling agent), and then placed in a metal layer forming solution as a mass fraction of 1%.
  • a surfactant in this example, a silane coupling agent
  • Chloroauric acid: 0.2 mol/L potassium carbonate 3:1 (volume ratio) in a mixed solution.
  • a direct current electrochemical reaction was carried out at room temperature to form a gold layer as a metal layer on the surface of the composite microspheres coated with the 3D graphene layer.
  • gold layers of different thicknesses for example, 10-100 nm
  • the conductive particles thus obtained are taken out from the metal layer forming solution by suction filtration, thereby realizing the conductive particles as shown in Fig. 1A.
  • the surfactant is not limited to a silane coupling agent and may be other surfactants.
  • the disclosure is not enumerated here.
  • Other conditions and parameters that can be conceived by those skilled in the art after reading this disclosure are also considered to be within the scope of the present disclosure.
  • This example is the same as the above-described Example 1 except that the order of the 3D graphene layer coating step and the gold layer coating step is reversed. Thereby, conductive particles as shown in FIG. 1B are realized.
  • This example is the same as the above Example 1 except that the material of the core microspheres is polyvinyl chloride. Thereby, the conductive particles as shown in FIG. 1A are realized.
  • This example is the same as the above Example 2 except that the material of the core microspheres is polyvinyl chloride. Thereby, conductive particles as shown in FIG. 1B are realized.
  • This example is the same as the above Example 1 except that the conductive monomer is a pyrrole monomer. Thereby, the conductive particles as shown in FIG. 1A are realized.
  • This example is the same as the above Example 1 except that the core microspheres are SiO 2 and the surfactant is a chromium complex coupling agent. Thereby, the conductive particles as shown in FIG. 1A are realized.
  • This example is the same as the above-described Example 1 except that the metal layer forming solution used was a silver formaldehyde-silver ammonia solution and an electroless silver plating layer was used as the metal layer.
  • the metal layer forming solution used was a silver formaldehyde-silver ammonia solution and an electroless silver plating layer was used as the metal layer.
  • reaction formula of electroless silver plating is as follows:
  • the reducing liquid can be first poured into the activation liquid carrying the microspheres after activation, and after the remaining Ag + in the activation liquid is completely reacted, the silver liquid is slowly added, and the reaction is completed and the silver layer is coated.
  • Composite microspheres When silver plating, the reducing liquid can be first poured into the activation liquid carrying the microspheres after activation, and after the remaining Ag + in the activation liquid is completely reacted, the silver liquid is slowly added, and the reaction is completed and the silver layer is coated. Composite microspheres.
  • Embodiments of the present disclosure also provide a conductive paste comprising the conductive particles according to the above.
  • the conductive paste is prepared by uniformly distributing the above-mentioned conductive particles in an insulating rubber material.
  • the embodiment of the present disclosure forms conductive particles by coating a surface of a core microsphere with a conductive polymer layer and coating a surface of the conductive polymer layer with a 3D graphene layer and a metal layer. Since the 3D graphene layer has extremely high pressure resistance and the conductive polymer layer has high conductivity, it is possible to maintain the conductive strength of the conductive particles while maintaining the conductive function of the conductive particles. Thereby, it is ensured that the conductive paste is used over a wider pressure range, and the time consumption per unit product is reduced, the cost is reduced, and the productivity is increased.
  • the embodiments of the present disclosure are not limited to solving the problem that the conductive particles are broken during the use of the conductive adhesive, and are also applicable to the problem of the breakage of the conductive particles in the electronic field, thereby reducing the rework rate and the production cost, and improving the yield.

Abstract

一种导电粒子及其制造方法以及包括该导电粒子的导电胶及其制造方法。该导电粒子包括：核芯微球（10）；包覆核芯微球（10）的导电高分子层（12）；以及包覆导电高分子层（12）的3D石墨烯层（14）和金属层（16）。该导电胶包括该导电粒子。该导电粒子和导电胶可以在提高耐压强度的同时保持导电功能。

Description

导电粒子及其制造方法以及导电胶及其制造方法
本申请要求于2016年5月31日递交的中国专利申请第201610371467.6号的优先权，在此全文引用上述中国专利申请公开的内容以作为本申请的一部分。
技术领域
本公开的实施例涉及导电粒子及其制造方法以及包括导电粒子的导电胶及其制造方法。
背景技术
目前导电胶被广泛应用于电子封装领域。导电胶主要包含导电粒子和绝缘胶材。导电粒子是导电胶中起到导通作用的关键成分。导电粒子的材质主要有两种：金属粉末、以及表面涂布金属的高分子微球。
目前，在导电胶使用过程中由于挤压强度问题会造成导电粒子的破裂，导致出现产品划伤、功能不良等问题。当该导电胶为各向异性导电胶膜(Anisotropic Conductive Film)时，还会导致失去各向异性导通功能的问题。为此，需要对导电粒子进行返修。然而，导电粒子返修成功率不是很高，这导致单位产品工时增加，影响产品良率，提高了单位产品成本。为了降低单位产品成本，进一步扩大导电胶的使用范围，现有技术中存在对耐压能力更高的导电粒子和导电胶的需求。
发明内容
本公开的实施例提供一种新型导电粒子及其制造方法以及包括所述导电粒子的导电胶及其制造方法，可以在提高导电粒子的耐压强度的同时保持导电粒子的导电功能。此种新型导电粒子的结构可保证在更宽压力范围使用导电胶，使得导电胶的适用范围更广。并且，可以减少单位产品耗时，降低成本，并提高产能。
根据本公开实施例的第一方面，提供一种导电粒子，其包括：
核芯微球；
包覆所述核芯微球的导电高分子层；以及
3D石墨烯层和金属层，其包覆所述导电高分子层。
根据该方面，在导电粒子的核芯微球的表面包覆导电高分子层并且在导电高分子层的表面包覆3D石墨烯层和金属层。由于3D石墨烯层具有极高耐压性并且导电高分子层具有高导电性，可以在提高导电粒子的耐压强度的同时保持导电粒子各向异性导电功能。从而，保证在更宽压力范围使用导电胶，并且减少单位产品耗时，降低成本，并提高产能。
根据本公开的一个示例性实施例，所述3D石墨烯层包覆所述导电高分子层，所述金属层包覆所述3D石墨烯层。根据该实施例，通过使核芯微球的表面被导电高分子层包覆，导电高分子层的表面被3D石墨烯层包覆，并且3D石墨烯层的表面被金属层包覆，即，在核芯微球与金属层之间增加导电高分子层和3D石墨烯层，可以在提高导电粒子的耐压强度的同时保持导电粒子的导电功能，从而保证在更宽压力范围使用导电胶。
根据本公开的另一个示例性实施例，所述金属层包覆所述导电高分子层，所述3D石墨烯层包覆所述金属层。根据该实施例，通过使核芯微球的表面被导电高分子层包覆，导电高分子层的表面被金属层包覆，并且金属层的表面被3D石墨烯层包覆，可以在提高导电粒子的耐压强度的同时保持导电粒子导电功能，从而保证在更宽压力范围使用导电胶。
根据本公开的示例性实施例，所述核芯微球为单分散性聚苯乙烯微球。根据该示例性实施例，由于聚苯乙烯具有轻质、粒径可控的特点，由此制成的导电粒子和导电胶也具有轻质、粒径可控的优点。并且，聚苯乙烯微球容易获得，能够降低产品成本。
根据本公开的示例性实施例，所述导电高分子层为聚苯胺层。根 据该示例性实施例，由于聚苯胺具有高导电率且合成简单，因此最终形成的导电粒子即使在高挤压轻度下也能保持高的导电功能，并且可以降低生产成本。
根据本公开的示例性实施例，所述金属层为金层。根据该示例性实施例，采用金作为金属层的材料，即使金层厚度很小，也可以确保导电粒子的导电性能。
根据本公开的示例性实施例，所述核芯微球的平均直径为0.1μm-10μm。根据该示例性实施例，利用落在此范围内的平均直径的核芯微球制造导电粒子以及导电胶，可以使所形成的导电粒子和导电胶的导电性更佳，并且可以避免核芯微球的团聚而使得导电高分子层完整地包覆核芯微球。
根据本公开实施例的第二方面，提供一种导电粒子的制造方法，包括：
用导电高分子层包覆核芯微球的表面，从而得到复合微球；以及
用3D石墨烯层和金属层包覆所述复合微球的表面。
根据该方面，在导电粒子的核芯微球的表面包覆导电高分子层并且在导电高分子层的表面包覆3D石墨烯层和金属层。由于3D石墨烯层具有极高耐压性并且导电高分子层具有高导电性，可以在提高导电粒子的耐压强度的同时保持导电粒子导电功能。从而，保证在更宽压力范围使用导电胶，并且减少单位产品耗时，降低成本，并提高产能。
根据本公开的示例性实施例，所述用导电高分子层包覆核芯微球的表面包括以下步骤：
用表面活性剂处理所述核芯微球；以及
使导电单体经引发剂在所述核芯微球的表面发生聚合形成导电高分子层。
根据该实施例，可以在核芯微球的表面上简单、高效地形成具有高电导率的高分子层。由此，最终形成的导电粒子即使在高挤压强度下也能保持高的导电功能，并且可以降低生产成本。
根据本公开的一个示例性实施例，所述用3D石墨烯层和金属层包覆所述复合微球的表面包括：
用所述3D石墨烯层包覆所述复合微球的表面；以及
用所述金属层包覆所述3D石墨烯层的表面。
根据该实施例，通过使核芯微球的表面被导电高分子层包覆，导电高分子层的表面被3D石墨烯层包覆，并且3D石墨烯层的表面被金属层包覆，即，在核芯微球与金属层之间增加导电高分子层和3D石墨烯层，可以在提高导电粒子的耐压强度的同时保持导电粒子的导电功能，从而保证在更宽压力范围使用导电胶。
根据本公开的示例性实施例，所述用所述3D石墨烯层包覆所述复合微球的表面包括：
用石墨烯层包覆多孔SiO2表面且然后进行HF湿法蚀刻，得到3D石墨烯粉；以及
对所述3D石墨烯粉进行分散，并且在分散后的所述3D石墨烯粉中加入所述复合微球，从而得到被3D石墨烯层包覆的复合微球。
根据该实施例，通过利用成熟的微加工工艺方便、容易地形成3D石墨烯层，从而可以降低导电粒子的成本。
根据本公开的示例性实施例，所述用金属层包覆所述3D石墨烯层的表面包括：
将所述被3D石墨烯层包覆的复合微球置于金属层形成溶液中，经电化学作用在所述被3D石墨烯层包覆的复合微球表面形成金属层，从而得到所述导电粒子。
根据该实施例，通过在被3D石墨烯层包覆的复合微球表面形成金属层，可以提高导电粒子的导电性能。
根据本公开的另一个示例性实施例，所述用3D石墨烯层和金属层包覆所述复合微球的表面包括：
用所述金属层包覆所述复合微球的表面；以及
用所述3D石墨烯层包覆所述金属层的表面。
根据该实施例，通过使核芯微球的表面被导电高分子层包覆，导电高分子层的表面被金属层包覆，并且金属层的表面被3D石墨烯层包覆，可以在提高导电粒子的耐压强度的同时保持导电粒子导电功能，从而保证在更宽压力范围使用导电胶。
根据本公开的示例性实施例，所述用所述金属层包覆所述复合微球的表面包括：
将所述复合微球置于金属层形成溶液中，经电化学作用在所述复合微球的表面形成金属层，从而得到被金属层包覆的复合微球。
根据该实施例，通过在复合微球表面形成金属层，可以提高导电粒子的导电性能。
根据本公开的示例性实施例，所述用所述3D石墨烯层包覆所述金属层的表面包括：
用石墨烯层包覆多孔SiO2表面且然后进行HF湿法蚀刻，得到3D石墨烯粉；以及
对所述3D石墨烯粉进行分散，并且在分散后的所述3D石墨烯粉中加入所述被金属层包覆的复合微球，从而得到所述导电粒子。
根据该实施例，通过利用成熟的微加工工艺方便、容易地形成3D石墨烯层，从而可以降低导电粒子的成本。
根据本公开的示例性实施例，所述核芯微球为单分散性聚苯乙烯微球。根据该示例性实施例，由于聚苯乙烯具有轻质、粒径可控的特点，由此制成的导电粒子和导电胶也具有轻质、粒径可控的优点。并且，聚苯乙烯微球容易获得，能够降低产品成本。
根据本公开的示例性实施例，所述导电高分子层为聚苯胺层。根据该示例性实施例，由于聚苯胺具有高导电率且合成简单，因此最终形成的导电粒子即使在高挤压轻度下也能保持高的导电功能，并且可以降低生产成本。
根据本公开的示例性实施例，所述金属层为金层。根据该示例性实施例，采用金作为金属层的材料，即使金层厚度很小，也可以确保 导电粒子的导电性能。
根据本公开的示例性实施例，所述核芯微球的平均直径为0.1μm-10μm。根据该示例性实施例，利用落在此范围内的平均直径的核芯微球制造导电粒子以及导电胶，可以使所形成的导电粒子和导电胶的导电性更佳，并且可以避免核芯微球的团聚而使得导电高分子层完整地包覆核芯微球。
根据本公开的示例性实施例，所述表面活性剂为两性偶联剂，包括但不限于铬络合物偶联剂、硅烷偶联剂、钛酸酯偶联剂、含锆偶联剂。
根据本公开的第三方面，提供一种导电胶，包括根据第一方面所述的导电粒子。
根据该方面，由于包括第一方面的导电粒子并且所述导电粒子能够在提高其耐压强度的同时保持其导电功能，因此该导电胶可以在更宽压力范围使用，并且可以降低成本，并提高产能。
根据本公开的第三方面，提供一种导电胶的制造方法，包括使第一方面的导电粒子均匀地分布在绝缘胶材中的步骤。
根据该方面，通过使第一方面的导电粒子均匀地分布在绝缘胶材中而制备导电胶。由于其中的导电粒子在提高其耐压强度的同时保持其导电功能，因此可以提供能够在更宽压力范围使用的导电胶，并且可以降低成本，并提高产能。
由上述技术方案可知，本公开实施例通过在核芯微球的表面包覆导电高分子层并且在导电高分子层的表面包覆3D石墨烯层和金属层，形成导电粒子，并进而采用该导电粒子形成导电胶。由于3D石墨烯层具有极高耐压性并且导电高分子层具有高导电性，可以在提高导电粒子的耐压强度的同时保持导电粒子导电功能。从而，保证在更宽压力范围使用导电胶，并且减少单位产品耗时，降低成本，并提高产能。
附图说明
为了更清楚地说明本公开实施例中的技术方案，下面将对实施例描述中所需要使用的附图作一简单地介绍。显而易见地，下面描述中的附图仅涉及本公开的一些实施例，而非对本公开的限制。公开。
图1A是根据本公开的一个示例性实施例的导电粒子的剖面图；
图1B是根据本公开的另一个示例性实施例的导电粒子的剖面图；
图2A是根据本公开的一个示例性实施例制造图1A所示的导电粒子的流程示意图；以及
图2B是根据本公开的另一个示例性实施例制造图1B所示的导电粒子的流程示意图。
具体实施方式
为使本公开实施例的目的、技术方案和优点更加清楚，下面将结合本公开实施例中的附图，对本公开实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本公开一部分实施例，而不是全部的实施例。基于本公开中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本公开保护的范围。
根据本公开的示例性实施例，提供了一种新型导电粒子。该新型导电粒子包括核芯微球、包覆核芯微球的导电高分子层、以及包覆导电高分子层的3D石墨烯层和金属层。
图1A是根据本公开的一个示例性实施例的导电粒子的剖面图。如图1A所示，该导电粒子包括核芯微球10、包覆核芯微球10的导电高分子层12、包覆导电高分子层12的3D石墨烯层14、以及包覆3D石墨烯层14的金属层16。
图1B是根据本公开的另一个示例性实施例的导电粒子的剖面图。如图1B所示，该导电粒子包括核芯微球10、包覆核芯微球10的导电高分子层12、包覆导电高分子层12的金属层16、以及包覆金属层16的3D石墨烯层14。
作为核芯微球10，可以采用诸如聚氯乙烯、聚苯乙烯等的高分子材料或诸如SiO2、TiO2等的无机材料的微米或纳米微球。在这些材料当中，优 选使用单分散性聚苯乙烯微球。由于聚苯乙烯具有轻质、粒径可控的特点，由此制成的导电粒子和导电胶也具有轻质、粒径可控的优点。并且，聚苯乙烯微球容易获得，能够降低产品成本。
对于核芯微球10的直径没有特别的限制。导电胶的导电性取决于导电粒子的传导性，在确保导电传导的前提下，导电粒子的粒径越小，所形成的导电胶导电性越佳。优选地，作为导电粒子的形成基础结构的核芯微球10的平均直径小于等于10μm。另一方面，如果核芯微球10的直径过小，则有可能发生核芯微球10的团聚。为了避免核芯微球10的团聚以使得导电高分子层12完整地包覆核芯微球10，优选核芯微球的平均直径大于等于0.1μm。
作为导电高分子层12，可以采用诸如聚吡咯、聚对苯撑、聚苯硫醚、聚苯胺等的导电高分子材料。优选地，由于合成简单、成本低、导电率高，优选采用聚苯胺作为导电高分子层12的材料。
对于导电高分子层12的厚度没有特别的限制。例如，导电高分子层12的厚度可以为100-500nm。
对于3D石墨烯层14的厚度没有特别的限制。例如，3D石墨烯层14的厚度可以为50-200nm。
作为金属层16，可以采用诸如金、银、铜等金属材料或其合金材料。优选地，采用金作为金属层16的材料，即使金层厚度很小，也可以确保导电粒子的导电性能。
对于金属层16的厚度没有特别的限制。例如，金属层16的厚度可以为10-100nm。
根据本公开的示例性实施例，还提供了一种导电粒子的制造方法。该制造方法包括：
用导电高分子层包覆核芯微球的表面，从而得到复合微球；以及
用3D石墨烯层和金属层包覆所述复合微球的表面。
根据一个示例性实施例，所述用3D石墨烯层和金属层包覆所述复合微球的表面包括用所述3D石墨烯层包覆所述复合微球的表面以及用所述金 属层包覆所述3D石墨烯层的表面，以得到图1A所示的导电粒子。
根据另一个示例性实施例，所述用3D石墨烯层和金属层包覆所述复合微球的表面包括用所述金属层包覆所述复合微球的表面以及用所述3D石墨烯层包覆所述金属层的表面，以得到图1B所示的导电粒子。
图2A是根据本公开的一个示例性实施例制造图1A所示的导电粒子的流程示意图。
如图2A所示，首先，在步骤S210中，用导电高分子层12包覆核芯微球10的表面。例如，该步骤可以具体地包括：用表面活性剂处理核芯微球10，以及使导电单体经引发剂在核芯微球的表面聚合为导电高分子层12，从而得到复合微球。
在此，表面活性剂可以为两性偶联剂，包括但不限于铬络合物偶联剂、硅烷偶联剂、钛酸酯偶联剂、含锆偶联剂等。
接下来，在步骤S212中，用3D石墨烯层14包覆复合微球的表面。例如，该步骤可以具体地包括：用石墨烯层包覆多孔SiO2表面，然后进行HF湿法蚀刻，得到3D石墨烯粉；以及对3D石墨烯粉经分散液进行均匀分散，并且在分散后的3D石墨烯粉中加入复合微球，从而得到被3D石墨烯层14包覆的复合微球。
然后，在步骤S214中，用金属层16包覆3D石墨烯层14的表面。例如，该步骤可以具体地包括：将被3D石墨烯层14包覆的复合微球置于金属层形成溶液中，经电化学作用在被3D石墨烯层14包覆的复合微球表面形成金属层16，从而得到本实施例的导电粒子。
图2B是根据本公开的另一个示例性实施例制造图1B所示的导电粒子的流程的示意图。
如图2B所示，首先，在步骤S220中，用导电高分子层12包覆核芯微球10的表面。例如，该步骤可以具体地包括：用表面活性剂处理核芯微球10，以及使导电单体经引发剂在核芯微球的表面聚合为形成导电高分子层12，从而得到复合微球。
接下来，在步骤S222中，用金属层16包覆复合微球的表面。例如，该 步骤可以具体地包括：将复合微球置于金属层形成溶液中，经电化学作用在复合微球的表面形成金属层16，从而得到被金属层16包覆的复合微球。
然后，在步骤S224中，用3D石墨烯层14包覆金属层16的表面。例如，该步骤可以具体地包括：用石墨烯层包覆多孔SiO2表面，然后进行HF湿法蚀刻，得到3D石墨烯粉；以及对3D石墨烯粉经分散液进行均匀分散，并且在分散后的3D石墨烯粉中加入被金属层16包覆的复合微球，从而得到本实施例的导电粒子。
根据本公开的示例性实施例，还提供了一种包括上述导电粒子的导电胶。
对导电胶的类型不做具体限制，该导电胶可以为各方同性导电胶或各方异性导电胶。
根据本公开的示例性实施例，还提供了一种导电胶的制造方法，该制造方法包括使上述导电粒子均匀地分布在绝缘胶材中的步骤。
具体而言，可以以合适的配比使上述导电粒子均匀地分布在绝缘胶材中。根据导电胶的不同要求和规格，导电粒子与绝缘胶材的配比可以不同。
下面将结合具体的实例描述本公开实施例的导电粒子的制造方法。然而，本领域技术人员将理解，这些实例仅仅是为了示例本公开的实施例而给出的，并非为了限制本公开。
实例1
作为核芯微球，使用单分散性的平均直径为2μm的聚苯乙烯微球。
将聚苯乙烯微球加入到作为表面活性剂的硅烷偶联剂(例如，KH-550等)中，油浴温度140℃条件下反应40min后，经离心过滤得到经表面活性剂处理的微球。
将上述经表面活性剂处理的聚苯乙烯微球置于盐酸溶液中磁力搅拌一段时间。然后，在逐滴加入作为导电单体的苯胺单体并搅拌一段时间后，苯胺单体吸附在聚苯乙烯微球表面。接下来，逐滴加入作为引发剂的过硫酸铵和碘酸钾，使得苯胺单体在聚苯乙烯微球表面发生聚合。反应结束后，即在聚苯乙烯微球表面形成一层聚苯胺导电层。通过控制单体用量，可将 聚苯胺导电层控制在100-500nm。由此，得到复合微球。
接下来，在温度为1100℃，CH4、H2、Ar环境下，通过化学气相沉积(CVD)在作为模板的多孔SiO2表面沉积石墨烯层。待冷却至室温后，将产品浸没到HF液中以进行各向同性刻蚀而完全去除多孔SiO2模板，得到3D石墨烯粉末。然后，在2250℃条件下对3D石墨烯粉末干燥并进行退火。
可选地，可以以如上得到的石墨烯层为模板，通过CVD再次沉积石墨烯，由此可根据需要得到不同厚度的3D石墨烯。可根据需求调节条件而得到不同厚度的3D石墨烯层。
这里，根据所使用的诸如多孔SiO2模板的形状，3D石墨烯粉末可以为柱状、球形、方形等。
接下来，将上述3D石墨烯粉末加入到作为分散液的表面活性剂(在本实例中，为硅烷偶联剂)的水溶液中进行分散。在分散液将3D石墨烯粉末均匀分散后，在上述分散体系中加入在聚苯胺层表面经表面活性剂处理的复合微球。然后，通过离心分层抽滤，得到被3D石墨烯层包覆的复合微球。通过控制分散液中石墨烯的固含量，可得到不同厚度的3D石墨烯层(例如，50-200nm)。
接下来，对上述被3D石墨烯层包覆的复合微球进行表面活性剂(在本实例中，为硅烷偶联剂)处理，然后将其置于作为金属层形成溶液的质量分数为1％的氯金酸：0.2mol/L的碳酸钾＝3:1(体积比)的混合溶液中。在室温下进行直流电化学反应，在被3D石墨烯层包覆的复合微球表面形成作为金属层的金层。通过调整反应条件，可实现不同厚度(例如，10-100nm)的金层。由此得到的导电粒子通过抽滤而从金属层形成溶液中取出，从而实现如图1A所示的导电粒子。
本领域技术人员将理解，在本实例中给出的各步骤中使用的具体条件和参数仅仅是一个例子。本领域技术人员可以根据实际需要设计不同的条件和参数。例如，表面活性剂不限于硅烷偶联剂，可以为其他表面活性剂。金属层形成溶液不限于质量分数为1％的氯金酸：0.2mol/L的碳酸钾＝3:1(体积比)的混合溶液，而是可以为包含其他组分(例如，柠檬酸钠和氯 金酸)的其他比例的混合溶液。本公开在此不进行一一列举。本领域技术人员在阅读本公开之后所能想到的其他条件和参数，也被视为在本公开的范围内。
实例2
除了将3D石墨烯层包覆步骤和金层包覆步骤的顺序颠倒之外，本实例与上述实例1相同。从而，实现如图1B所示的导电粒子。
实例3
除了核芯微球的材料为聚氯乙烯之外，本实例与上述实例1相同。从而，实现如图1A所示的导电粒子。
实例4
除了核芯微球的材料为聚氯乙烯之外，本实例与上述实例2相同。从而，实现如图1B所示的导电粒子。
实例5
除了导电单体为吡咯单体之外，本实例与上述实例1相同。从而，实现如图1A所示的导电粒子。
实例6
除了核芯微球为SiO2，并且表面活性剂为铬络合物偶联剂之外，本实例与上述实例1相同。从而，实现如图1A所示的导电粒子。
实例7
除了所使用的金属层形成溶液为银甲醛—银氨溶液而化学镀银层作为金属层之外，本实例与上述实例1相同。
其中，化学镀银的反应式如下：
2[Ag(NH3)2]OH+HCHO→2Ag+4NH3↑+HCOOH+H2O
镀银时,可以将还原液首先倒入活化后载有微球的活化液中,待活化液中剩余的Ag+反应完全后,再缓慢加入银液，反应结束即得到被银层包覆的复合微球。
本公开实施例还提供一种导电胶，其包括根据上述导电粒子。通过使上述导电粒子均匀地分布在绝缘胶材中，来制成导电胶。
如上所述，本公开实施例通过在核芯微球的表面包覆导电高分子层并且在导电高分子层的表面包覆3D石墨烯层和金属层而形成导电粒子。由于3D石墨烯层具有极高耐压性并且导电高分子层具有高导电性，可以在提高导电粒子的耐压强度的同时保持导电粒子导电功能。从而，保证在更宽压力范围使用导电胶，并且减少单位产品耗时，降低成本，并提高产能。
此外，本公开实施例不限于解决导电胶使用过程中导电粒子破裂的问题，也适用于电子领域中的导电粒子破裂问题，从而降低返工率和生产成本，提高良率。
本公开的说明书中，说明了大量具体细节。然而，能够理解，本公开的实施例可以在没有这些具体细节的情况下实践。在一些实例中，并未详细示出公知的方法、结构和技术，以便不模糊对本说明书的理解。
最后应说明的是：以上实施例仅用以说明本公开的技术方案，而非对其限制；尽管参照前述实施例对本公开进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本公开各实施例技术方案的精神和范围。

Claims (22)

  1. 一种导电粒子，包括：
    核芯微球；
    包覆所述核芯微球的导电高分子层；以及
    3D石墨烯层和金属层，其包覆所述导电高分子层的。
  2. 根据权利要求1所述的导电粒子，其中，所述3D石墨烯层包覆所述导电高分子层，所述金属层包覆所述3D石墨烯层。
  3. 根据权利要求1所述的导电粒子，其中，所述金属层包覆所述导电高分子层，所述3D石墨烯层包覆所述金属层。
  4. 根据权利要求1至3中任一项所述的导电粒子，其中，所述核芯微球为单分散性聚苯乙烯微球。
  5. 根据权利要求1至3中任一项所述的导电粒子，其中，所述导电高分子层为聚苯胺层。
  6. 根据权利要求1至3中任一项所述的导电粒子，其中，所述金属层为金层。
  7. 根据权利要求1至3中任一项所述的导电粒子，其中，所述核芯微球的平均直径为0.1μm-10μm。
  8. 一种导电粒子的制造方法，包括：
    用导电高分子层包覆核芯微球的表面，从而得到复合微球；以及
    用3D石墨烯层和金属层包覆所述复合微球的表面。
  9. 根据权利要求8所述的制造方法，其中，所述用导电高分子层包覆核芯微球的表面包括以下步骤：
    用表面活性剂处理所述核芯微球；以及
    使导电单体经引发剂在所述核芯微球的表面发生聚合形成导电高分子层。
  10. 根据权利要求9所述的制造方法，其中，所述用3D石墨烯层和金属层包覆所述复合微球的表面包括：
    用所述3D石墨烯层包覆所述复合微球的表面；以及
    用所述金属层包覆所述3D石墨烯层的表面。
  11. 根据权利要求10所述的制造方法，其中，所述用所述3D石墨烯层包覆所述复合微球的表面包括：
    用石墨烯层包覆多孔SiO2表面，然后进行HF湿法蚀刻，得到3D石墨烯粉；以及
    对所述3D石墨烯粉进行分散，并且在分散后的所述3D石墨烯粉中加入所述复合微球，从而得到被3D石墨烯层包覆的复合微球。
  12. 根据权利要求11所述的制造方法，其中，所述用金属层包覆所述3D石墨烯层的表面包括：
    将所述被3D石墨烯层包覆的复合微球置于金属层形成溶液中，经电化学作用在所述被3D石墨烯层包覆的复合微球表面形成金属层，从而得到所述导电粒子。
  13. 根据权利要求9所述的制造方法，其中，所述用3D石墨烯层和金属层包覆所述复合微球的表面包括：
    用所述金属层包覆所述复合微球的表面；以及
    用所述3D石墨烯层包覆所述金属层的表面。
  14. 根据权利要求13所述的制造方法，其中，所述用所述金属层包覆所述复合微球的表面包括：
    将所述复合微球置于金属层形成溶液中，经电化学作用在所述复合微球的表面形成金属层，从而得到被金属层包覆的复合微球。
  15. 根据权利要求14所述的制造方法，其中，所述用所述3D石墨烯层包覆所述金属层的表面包括：
    用石墨烯层包覆多孔SiO2表面，然后进行HF湿法蚀刻，得到3D石墨烯粉；以及
    对所述3D石墨烯粉进行分散，并且在分散后的所述3D石墨烯粉中加入所述被金属层包覆的复合微球，从而得到所述导电粒子。
  16. 根据权利要求8至15中任一项所述的制造方法，其中，所述核芯微球为单分散性聚苯乙烯微球。
  17. 根据权利要求8至15中任一项所述的制造方法，其中，所述导电高分子层为聚苯胺层。
  18. 根据权利要求8至15中任一项所述的制造方法，其中，所述金属层为金层。
  19. 根据权利要求8至15中任一项所述的制造方法，其中，所述核芯微球的平均直径为0.1μm-10μm。
  20. 根据权利要求9至15中任一项所述的制造方法，其中，所述表面活性剂为铬络合物偶联剂、硅烷偶联剂、钛酸酯偶联剂、含锆偶联剂。
  21. 一种导电胶，包括根据权利要求1至7中任一项所述的导电粒子。
  22. 一种导电胶的制造方法，包括使根据权利要求1至7中任一项所述的导电粒子均匀地分布在绝缘胶材中的步骤。
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