WO2020239143A1 - 一种石墨烯导电油墨及其制备方法 - Google Patents

一种石墨烯导电油墨及其制备方法 Download PDF

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WO2020239143A1
WO2020239143A1 PCT/CN2020/103705 CN2020103705W WO2020239143A1 WO 2020239143 A1 WO2020239143 A1 WO 2020239143A1 CN 2020103705 W CN2020103705 W CN 2020103705W WO 2020239143 A1 WO2020239143 A1 WO 2020239143A1
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graphene
conductive ink
alcohol
graphene conductive
grinding
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French (fr)
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陈国华
邱欣斌
刘飞翔
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华侨大学
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/19—Preparation by exfoliation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/20—Graphite
    • C01B32/21—After-treatment
    • C01B32/22—Intercalation
    • C01B32/225—Expansion; Exfoliation
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/023—Emulsion inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
    • C01B2204/22—Electronic properties

Definitions

  • the invention belongs to the technical field of graphene, and specifically relates to a graphene conductive ink and a preparation method thereof.
  • Conductive ink is a type of composite material composed of conductive fillers, binders, solvents and various auxiliary additives. Conductive fillers are the key phase that affects the performance of conductive inks. In the conductive ink, there are countless conductive particles uniformly dispersed in the binder and ink solvent. The liquid conductive ink is in an insulating state. The conductive pattern or printed film obtained after the conductive ink is printed, and the printed product obtained after annealing has a certain degree of conductivity .
  • the conductive polymer (represented by the PEDOT/PSS system) conductive ink has poor stability and low conductivity, and the PEDOT/PSS polymer conductive ink needs to be appropriately doped and has poor weather resistance.
  • Special functional electronic devices prepared based on graphene conductive inks have their unique advantages over earlier printed conductive inks: corrosion resistance, flexibility, lightweight, low cost, and environmental protection.
  • graphene conductive inks have been involved in various applications including: flexible electronic screens, functional sensors, photovoltaic cells, printed microcircuits, radio frequency identification devices (RFID), and so on.
  • RFID radio frequency identification devices
  • the widespread use of RFID which has attracted much attention at home and abroad, relies on the unique advantages of graphene conductive ink products such as low cost, industrialization, and green environmental protection, laying a certain foundation for the era of flexible electronics.
  • Graphene as a new generation of conductive material, has unparalleled high charge mobility. Kirill Bolotin from Columbia University measured the charge mobility of 2.5 ⁇ 10 5 cm 2 /(V ⁇ s) from graphene with a complete structure. It is 100 times that of single crystal silicon material and its charge mobility is not affected by temperature. Each carbon atom in the graphene structure provides an unbonded ⁇ electron and can move freely on the surface of the graphene crystal, giving it ultra-high electron mobility. Therefore, graphene as a conductive material has shown its wide application prospects in many fields such as energy storage, signal transmission, sensor detection, and composite materials.
  • the current preparation method of graphene conductive ink is mainly the liquid phase peeling method to prepare graphene conductive ink.
  • the liquid phase exfoliation method is mainly embodied by the use of the mechanism between the difference in surface energy (E s ) between graphene and organic solvents and the interlayer force of graphene: that is, the lower the difference in surface energy between graphene layers The smaller the van der Waals force, the surface energy of graphene (E SG ⁇ 70.0mJ ⁇ m -2 ) and the surface energy of dimethylformamide (DMF) (E S-DMF ⁇ 65.0mJ ⁇ m -2 ) and N-formaldehyde The surface energy of pyrrolidone (NMP) (E S-NMP ⁇ 68.2mJ ⁇ m -2 ) is relatively close.
  • the liquid phase exfoliation method mainly uses this type of solvent to perform rapid shear exfoliation of natural graphite to obtain graphene conductive fillers and prepare graphene conductive inks.
  • the preparation efficiency of this method is not high, the distribution of graphene sheets is large, the size of the sheet is different, and the toxicity of DMF and NMP solvents makes it not suitable for commercial applications.
  • the purpose of the present invention is to provide a graphene conductive ink.
  • Another object of the present invention is to provide a method for preparing the aforementioned graphene conductive ink.
  • a graphene conductive ink is composed of a self-stabilized dispersion graphene nano material, an alcohol-water mixed solvent and an ink binder in a mass ratio of 2 ⁇ 4:50 ⁇ 100:1 ⁇ 2.
  • the material is made of sodium p-aminobenzene sulfonate, natural flake graphite and alcohol-water mixed solvent through liquid phase exfoliation method.
  • the sodium p-aminobenzene sulfonate acts on graphite through ⁇ - ⁇ conjugation, physical adsorption and chemical grafting Olefin surface.
  • the mass ratio of the natural flake graphite to the sodium p-aminobenzene sulfonate is 1-5:1-10.
  • the mass ratio of the natural flake graphite to the sodium p-aminobenzene sulfonate is 1-2.
  • the alcohol-water mixed solvent is composed of water and lower alcohol in a volume ratio of 2:3.
  • the lower alcohol is at least one of ethanol, ethylene glycol, glycerol, isopropanol and n-butanol.
  • the lower alcohol is isopropanol.
  • the ink binder is one of polyvinyl alcohol, polyethylene glycol, acrylic resin, epoxy resin, polyurethane resin, hydroxypropyl methylcellulose and nitrocellulose. kind or several.
  • the graphene conductive ink is composed of a self-stabilizing dispersion graphene nanomaterial, an alcohol-water mixed solvent and an ink binder in a mass ratio of 2 ⁇ 4:50 ⁇ 100:1 ⁇ 2 .
  • the method for preparing the graphene conductive ink includes the following steps:
  • the grinding time is 12 to 24 hours
  • the medium is zirconia beads with a particle size of 2 to 3 mm.
  • the self-stable dispersed graphene nanomaterial in the graphene conductive ink of the present invention can ensure the stable existence of the graphene dispersion system in the conductive ink.
  • the printed film of the graphene conductive ink of the present invention has excellent conductivity, film-forming properties, and mechanical properties (flexibility).
  • the graphene conductive ink of the present invention has diverse solvent selectivity and good printing adaptability.
  • the solvent includes water, ethanol, ethylene glycol, glycerol, isopropanol, n-butanol, DMF, NMP or their mixed solvents.
  • the choice of solvents with different viscosities can obtain conductive inks with different viscosities, making graphene conductive inks suitable for various printing methods (drip coating, spin coating, inkjet printing or screen printing).
  • the graphene conductive ink of the present invention has the advantages of stable dispersion, high conductivity, excellent printing adaptability, and excellent flexibility, and is expected to be applied to printing various flexible electronic devices.
  • Figure 1 is a schematic diagram of the process of preparing self-stably dispersed graphene nanomaterials according to the present invention
  • Figure 2 shows the graphene conductive ink (20mg/mL) of the present invention with different solvents: water, ethanol (EA), ethylene glycol (EG), glycerol (GI), isopropanol (IPA), n-butanol (BA), N,N-dimethylformamide (DMF), and N-methylpyrrolidone (NMP) were used as dispersions to test the dispersion performance, and the dispersion results comparison chart after standing for two months;
  • EA ethanol
  • EG ethylene glycol
  • GI glycerol
  • IPA isopropanol
  • BA n-butanol
  • DMF N,N-dimethylformamide
  • NMP N-methylpyrrolidone
  • Figure 3 (a) is a graph of the pressure-conductivity test results of the self-stabilized dispersion graphene nanomaterial sheet prepared in Example 1 of the present invention; (b) is the graphene conductive film prepared in Example 1 of the present invention through bright A comparison chart of the number of drops-resistance test results of the conductive film prepared by the treatment, in which the size of the conductive film is 1cm ⁇ 1cm; (c) is the graphene conductive film prepared in Example 1 of the present invention and the commercial carbon black conductive film flexibility test Figure;
  • Figure 4 shows the graphene conductive ink prepared in Example 1 of the present invention printed on the PET substrate (a, b, c), glass substrate (d, e), nylon fiber (f, g), wire (h ), plant (i) and paper substrate (j), the obtained graphene composite conductive material, the composite conductive material is connected in the conductive path, the light emitting diode in the circuit can emit light (e, g, i, j) .
  • the conductive ink was applied to the PET substrate (a, b, c in Figure 4), glass substrate (d and e in Figure 4), nylon fibers (f and g in Figure 4), and wires (f and g in Figure 4) by drip coating.
  • the conductive ink is drip-coated on glass substrate, paper substrate, PET substrate, nylon fiber substrate, wire substrate and paper substrate by drip coating method, and placed in a constant temperature blast oven at 80°C for heating and drying to obtain graphene conductive graphene film ,
  • the formation of the thin film conductive path, the result is similar to Figure 4;
  • FIG. 1 a flow chart of the preparation of the self-dispersed and self-stabilized graphene nanomaterials in Examples 1 and 2 of the present invention.
  • the ⁇ - ⁇ conjugation of the conjugated SAS and the graphite surface further enhances the peeling efficiency;
  • the self-dispersed self-dispersed graphene nanomaterials are prepared by peeling off the graphite through the mechanical shearing action of the cyclic ball milling, which ensures the graphene conductive ink Dispersion stability: Centrifugal washing the self-stable dispersed graphene nanomaterials with stable dispersion on the upper layer to obtain key G-SAS conductive fillers.
  • Figure 2 shows the self-dispersing and self-stabilizing dispersion of graphene nanomaterial conductive fillers in water, ethanol, ethylene glycol, glycerol, n-butanol, isopropanol, DMF, NMP can achieve long-term stable dispersion for 2 months , Verifying its good dispersion adaptability.
  • the conductivity of the self-stabilized dispersed graphene nanomaterial conductive film in Figure 3 (a) is 2.60 ⁇ 10 4 S/m at a pressure of 25 kPa; the bright treatment in (b) is for simple drop coating to obtain improved film conductivity Larger, the graphene nanosheet layer is made denser, uniform and continuous through bright treatment; (c) The self-stabilized dispersion graphene nanomaterial conductive film still retains 79% conductivity after thousands of folds, while ordinary The carbon black conductive ink loses its conductivity after being folded 200 times due to the destruction of the conductive path.
  • Figure 4 shows the graphene conductive ink prepared in Example 1 of the present invention printed on the PET substrate (a, b, c), glass substrate (d, e), nylon fiber (f, g), wire (h ), plant leaves (i) and paper substrate (j), the obtained graphene composite conductive material, the composite conductive material is connected to the conductive path, the light emitting diode in the circuit can emit light (e, g, i, j ); It is verified that the self-stabilized dispersion graphene nanomaterial conductive material has excellent conductivity.
  • the graphene conductive ink and the preparation method thereof provided by the present invention can be prepared by a simple liquid phase peeling method to obtain the graphene conductive ink.
  • the liquid phase peeling process is simple and feasible, the conductive ink is green and environmentally friendly, and has a wide range of applications;
  • the self-dispersing graphene nanomaterial with self-dispersing ability can ensure the stable existence of the graphene dispersion system in the conductive ink and ensure the long-term effectiveness of the ink
  • the conductive ink has various solvent selectivity, including water, ethanol, ethylene glycol, glycerol, isopropanol, n-butanol, DMF, NMP, etc., with excellent printing adaptability;
  • the graphene conductive ink is printed conductive
  • the material has excellent electrical conductivity, film-forming properties, rheological properties and mechanical properties (flexibility). Therefore, the various characteristics exhibited by the graphene conductive ink of the present invention are expected

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Abstract

本发明公开了一种石墨烯导电油墨及其制备方法，由自稳定分散石墨烯纳米材料、醇水混合溶剂和墨水粘结剂以2～4:50～100:1～2的质量比组成，其中自稳定分散石墨烯纳米材料由对氨基苯磺酸钠、天然鳞片石墨和醇水混合溶剂通过液相剥离法制成，其中对氨基苯磺酸钠通过π-π共轭作用、物理吸附作用及化学接枝作用于石墨烯表面。本发明的石墨烯导电油墨稳定分散、高电导率、优异的印刷适应性、优异的柔性等优势有望应用于印刷各类柔性电子器件。

Description

一种石墨烯导电油墨及其制备方法
本申请要求于2019年5月27日提交中国专利局、申请号为201910444840.X、发明名称为“一种石墨烯导电油墨及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明属于石墨烯技术领域，具体涉及一种石墨烯导电油墨及其制备方法。
背景技术
导电油墨是一种由导电填料、粘结剂、溶剂和各类辅助助剂共同组成的一类复合材料，其中导电填料是影响导电油墨性能的关键相。导电油墨中有无数的导电粒子均匀分散于粘结剂和油墨溶剂中，液态的导电油墨处于绝缘状态，导电油墨印刷后获得的导电图案或印刷薄膜，经退火后获得的印刷产品具备一定导电性。
通过光刻、化学刻蚀、化学镀覆、真空沉积等方式所制备的传统电子器件及储能器件存在诸多缺陷：金属耗材昂贵、工艺繁杂、环境污染等等。20世纪90年代，导电油墨的发展初见端倪，在传统的硅基电子信息技术革新中，催生了现代电子印刷技术一印刷导电油墨。各类印刷导电油墨如金属系导电油墨、导电高分子系导电油墨以及碳系导电油墨如雨后春笋般迅猛发展。研究较为成熟的导电银浆导电性能优异且具备一定的应用，但银纳米粒子容易发生银迁移与沉降，且金属银价格昂贵有碍于其广泛应用。而另一类金属导电油墨导电铜浆作为成本较为低廉的导电油墨因铜纳米颗粒抗氧化性极差，极大地限制其应用与发展。另外，导电高分子系(以PEDOT/PSS系为代表)导电油墨稳定性差、导电性低、PEDOT/PSS高分子导电油墨需适当掺杂且耐候性差。基于石墨烯导电油墨制备的特种功能电子器件较于早前种类繁多的印刷导电油墨有着其独特的优势：耐腐蚀、可挠性、轻量化、低廉化、绿色环保等。随着石墨烯制备技术的发展，石墨烯导电油墨已经涉足各个领域应用包括：柔性电子屏、功能传感器、光伏电池、印刷微型电路以及无线射频识别设备(RFID)等等。尤其备受国内外瞩目的RFID的广泛运用，依仗石墨烯导电油墨产品具备低成本、可产 业化、绿色环保等独特优势，为柔性电子时代奠定一定的基础。
石墨烯作为新一代的导电材料，具备无与伦比的高电荷迁移率，来自哥伦比亚大学的Kirill Bolotin从结构完整的石墨烯中测得其电荷迁移率为2.5×10 5cm 2/(V·s)，是单晶硅材料的100倍之多且其电荷迁移率不受温度的影响。石墨烯结构中每个碳原子均提供一个未成键的π电子并能够在石墨烯晶体表面自由移动，赋予其超高的电子迁移率。因此石墨烯作为导电材料在储能、信号传输、传感器检测、复合材料等诸多领域展现出其广泛的应用前景。
目前石墨烯导电油墨的制备方法主要为液相剥离法制备石墨烯导电油墨。液相剥离法主要体现为利用石墨烯与有机溶剂之间的表面能(E s)差值和石墨烯的层间作用力之间存在的机制：即表面能差值越低石墨烯层间的范德华作用力越小，其中石墨烯表面能(E S-G≈70.0mJ·m -2)和二甲基甲酰胺表面能(DMF)(E S-DMF≈65.0mJ·m -2)与N-甲基吡咯烷酮表面能(NMP)(E S-NMP≈68.2mJ·m -2)之间较为接近。因此液相剥离法主要利用这类溶剂对天然石墨进行速剪切剥离获得石墨烯导电填料并以此制备石墨烯导电油墨。然而此法制备效率不高，石墨烯片层分布大，片径大小不一，且DMF和NMP溶剂毒性大导致其并不适用于商业化应用。近来也出现利用混合溶剂液相剥离石墨烯材料制备石墨烯导电油墨的报道，通过调控绿色溶剂乙醇与水之间的配比获得表面能与石墨烯相近的混合溶剂并以此剥离得到石墨烯。此法过程相对简单，且避免了有毒有害溶剂，然而对于石墨烯的分散性问题或者过多绝缘的表面活性剂的加入都将阻碍液相剥离法在导电油墨领域的应用。因此若能避免高沸点有毒溶剂与绝缘的表面活性剂的使用，制备一类具备溶剂安全环保、无表面活性剂、高稳定分散、高导电性、可印刷柔性薄膜的石墨烯导电油墨将推动下一代柔性电子器件的发展。
发明内容
本发明的目的在于提供一种石墨烯导电油墨。
本发明的另一目的在于提供上述石墨烯导电油墨的制备方法。
本发明的技术方案如下：
一种石墨烯导电油墨，由自稳定分散石墨烯纳米材料、醇水混合溶剂 和墨水粘结剂以2～4:50～100:1～2的质量比组成，所述自稳定分散石墨烯纳米材料由对氨基苯磺酸钠、天然鳞片石墨和醇水混合溶剂通过液相剥离法制成，所述对氨基苯磺酸钠通过π-π共轭作用、物理吸附作用及化学接枝作用于石墨烯表面。
在本发明的一个优选实施方案中，所述天然鳞片石墨与对氨基苯磺酸钠的质量比为1～5:1～10。
进一步优选的，所述天然鳞片石墨与对氨基苯磺酸钠的质量比为1～2:1～2。
在本发明的一个优选实施方案中，所述醇水混合溶剂由水和低级醇以2:3的体积比组成。
进一步优选的，所述低级醇为乙醇、乙二醇、丙三醇、异丙醇和正丁醇中的至少一种。
更进一步优选的，所述低级醇为异丙醇。
在本发明的一个优选实施方案中，所述墨水粘结剂为聚乙烯醇、聚乙二醇、丙烯酸树脂、环氧树脂、聚氨酯树脂、羟丙基甲基纤维素和硝化纤维素中的一种或几种。
在本发明的一个优选实施方案中，所述石墨烯导电油墨由自稳定分散石墨烯纳米材料、醇水混合溶剂和墨水粘结剂以2～4:50～100:1～2的质量比组成。
上述石墨烯导电油墨的制备方法，包括如下步骤：
(1)将天然鳞片石墨、醇水混合溶剂和对氨基苯磺酸钠混合后进行超声处理，获得对氨基苯磺酸钠完全溶解的石墨分散液；
(2)将上述石墨分散液送入研磨机进行研磨，获得研磨浆料；
(3)将上述研磨浆料用洗涤溶剂进行离心洗涤，获得沉淀，即为所述自稳定分散石墨烯纳米材料；
(4)将上述自稳定分散石墨烯纳米材料、粘结剂和醇水混合溶剂混合研磨，即得所述石墨烯导电油墨。
在本发明的一个优选实施方案中，所述研磨的时间为12～24h，介质为粒径为2～3mm的氧化锆珠。
本发明的有益效果是：
1、本发明的石墨烯导电油墨中的自稳定分散石墨烯纳米材料能够保证导电油墨中的石墨烯分散体系的稳定存在。
2、本发明的石墨烯导电油墨的印刷薄膜具备优异的导电性能、成膜性能、机械性能(柔性)。
3、本发明的石墨烯导电油墨的溶剂选择性多样、印刷适应性良好，其中溶剂包括水、乙醇、乙二醇、丙三醇、异丙醇、正丁醇、DMF、NMP或其混合溶剂，不同粘度溶剂的选择可获得不同粘度的导电油墨，使得石墨烯导电油墨适应于各类印刷方式(滴涂、旋涂、喷墨打印或丝网印刷的方式)。
4、本发明的石墨烯导电油墨稳定分散、高电导率、优异的印刷适应性、优异的柔性等优势有望应用于印刷各类柔性电子器件。
5、本发明的制备方法通过液相剥离法获得可自稳定分散石墨烯纳米材料，并以此制备稳定分散的石墨烯导电油墨，其中采用表面张力与石墨烯表面能相匹配的溶剂(V 异丙醇/V 水＝3/2)，降低石墨层间范德瓦尔斯力的作用；并通过具有共轭效应的对氨基苯磺酸钠SAS与石墨表面的π-π共轭作用，进一步提升剥离效率；此外通过循环球磨的机械剪切作用剥离石墨制备自稳定分散石墨烯纳米材料，保证了石墨烯导电油墨的分散稳定性。
说明书附图
图1为本发明制备自稳定分散石墨烯纳米材料的流程示意图；
图2为本发明的石墨烯导电油墨(20mg/mL)以不同的溶剂水、乙醇(EA)、乙二醇(EG)、丙三醇(GI)、异丙醇(IPA)、正丁醇(BA)、N,N-二甲基甲酰胺(DMF)、N-甲基吡咯烷酮(NMP)作为分散液进行分散性能测试，静置两个月后的分散性结果对比图；
图3(a)为本发明实施例1中所制备的自稳定分散石墨烯纳米材料压片的压力-电导率测试结果图；(b)为本发明实施例1制备的石墨烯导电薄膜通过光亮处理所制备导电薄膜的滴涂次数-电阻测试结果对比图，其中导电薄膜尺寸为1cm×1cm；(c)为本发明实施例1中所制备的石墨烯导电薄膜与商业炭黑导电薄膜柔性测试图；
图4为本发明实施例1的所制备的石墨烯导电油墨印刷在滴涂于PET基底(a，b，c)、玻璃基底(d，e)、尼龙纤维(f，g)、导线(h)、植物 (i)和纸基底(j)中，获得的石墨烯复合导电材料，将复合导电材料连接于导电通路之中，可使电路中的发光二极管发光(e，g，i，j)。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1
根据本发明公开的技术方案，进行以下操作：
精确称取以下质量份的原料：8000目天然鳞片石墨10g、对氨基苯磺酸钠10g、异丙醇240mL、蒸馏水160mL，将以上组分原料超声混合均匀，获得研磨液；
将所得的研磨液放入篮式研磨机中通过粒径为2.5mm的氧化锆球球磨24h，转速为2000rpm，并通入冷却水循环冷却；
从研磨机料桶中取出研磨过后的上层物料，利用异丙醇/水(V 异丙醇/V 水＝3/2)溶剂对物料进行离心洗涤5次，最后获得自稳定分散石墨烯纳米材料，具体制备流程如图1所示；
精确称取以下质量份的原料：自稳定分散石墨烯纳米材料5g、水性丙烯酸树脂乳液1.5g、异丙醇60mL、蒸馏水40mL，将以上组分原料超声混合均匀，获得墨水研磨液；
将所得的墨水研磨液放入篮式研磨机中通过粒径为2.5mm的氧化锆球球磨2h，转速为500rpm，并通入冷却水循环冷却。最后收集研磨浆料，最终获得所述石墨烯导电油墨；
通过滴涂法将导电油墨滴涂于PET基底(图4中a、b、c)、玻璃基底(图4中d和e)、尼龙纤维(图4中f和g)、导线(图4中h)、植物(图4中i)和纸基底(图4中j)中，并放置于80℃恒温鼓风烘箱中加热烘干，得到石墨烯导电石墨烯薄膜，薄膜导电通路的形成，如图4所示；
对获得导电薄膜进行分散性能以及导电性能(四探针电阻测试)测试，如图2与3所示。
实施例2
根据本发明公开的技术方案，进行以下操作：
精确称取以下质量份的原料：8000目天然鳞片石墨10g、对氨基苯磺 酸钠5g、异丙醇240mL、蒸馏水160mL，将以上组分原料超声混合均匀，获得研磨液；
将所得的研磨液放入篮式研磨机中通过粒径为2.5mm的氧化锆球球磨24h，转速为2000rpm，并通入冷却水循环冷却；
从研磨机料桶中取出研磨过后的上层物料，利用异丙醇/水(V 异丙醇/V 水＝3/2)溶剂对物料进行离心洗涤5次，最后获得自稳定分散石墨烯纳米材料，其制备流程如图1所示；
精确称取以下质量份的原料：自稳定分散石墨烯纳米材料1g、水性丙烯酸树脂乳液1g、异丙醇240mL、蒸馏水160mL，将以上组分原料超声混合均匀，获得墨水研磨液；
将所得的墨水研磨液放入篮式研磨机中通过粒径为2.5mm的氧化锆球球磨2h，转速为500rpm，并通入冷却水循环冷却。最后收集研磨浆料，最终获得所述石墨烯导电油墨；
通过滴涂法将导电油墨滴涂于玻璃基底、纸基底、PET基底、尼龙纤维基底、导线基底和纸基底，并放置于80℃恒温鼓风烘箱中加热烘干，得到石墨烯导电石墨烯薄膜，薄膜导电通路的形成，结果与图4类似；
对获得导电薄膜进行分散性能以及导电性能(四探针电阻测试)测试，结果与图2～3类似。
如图1所示，由本发明实施例1、2中的自分散的自稳定分散石墨烯纳米材料制备流程图。通过液相剥离法，采用通过采用表面张力与石墨烯表面能相匹配的溶剂(V 异丙醇/V 水＝3/2)，降低石墨层间范德瓦尔斯力的作用；并通过具有共轭效应的SAS与石墨表面的π-π共轭作用，进一步提升剥离效率；此外通过循环球磨的机械剪切作用剥离石墨制备自分散的自稳定分散石墨烯纳米材料，保证了石墨烯导电油墨的分散稳定性，将上层稳定分散的自稳定分散石墨烯纳米材料进行离心洗涤，获得关键的G-SAS导电填料。图2图中自分散自稳定分散石墨烯纳米材料导电填料在水、乙醇、乙二醇、丙三醇、正丁醇、异丙醇、DMF、NMP中均能实现2个月的长期稳定分散，验证了其分散适应性良好。图3(a)中的自稳定分散石墨烯纳米材料导电薄膜在压力为25kPa时，薄膜电导率达到2.60×10 4S/m；(b)中的光亮处理对于简单滴涂获得薄膜导电性能提升较 大，通过光亮处理使得石墨烯纳米片层更为致密、均一与连续；(c)中自稳定分散石墨烯纳米材料导电薄膜经历上千次的折叠后仍旧保留79％的电导率，而普通的炭黑导电油墨则因导电通路的破坏，在折叠200次后失去导电性能。图4为本发明实施例1的所制备的石墨烯导电油墨印刷在滴涂于PET基底(a，b，c)、玻璃基底(d，e)、尼龙纤维(f，g)、导线(h)、植物叶片(i)和纸基底(j)中，获得的石墨烯复合导电材料，将复合导电材料连接于导电通路之中，可使电路中的发光二极管发光(e，g，i，j)；验证了自稳定分散石墨烯纳米材料导电材料具备优异的导电性能。
综上所述，说明本发明提供的一种石墨烯导电油墨及其制备方法，能够通过简单液相剥离法制备得到石墨烯导电油墨。首先液相剥离工艺简单可行，导电油墨绿色环保，适应范围广；其次具备自分散能力的自稳定分散石墨烯纳米材料能够保证导电油墨中的石墨烯分散体系的稳定存在，保证墨水的长期有效性；另外，导电油墨的溶剂选择性多样，包括水、乙醇、乙二醇、丙三醇、异丙醇、正丁醇、DMF、NMP等，印刷适应性优良；最后，石墨烯导电油墨印刷导电材料具备优异的导电性能、成膜性能、流变性能和机械性能(柔性)等。因此，本发明石墨烯导电油墨所展现出的各类特性有望应用于印刷各类柔性电子器件。
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。

Claims (14)

  1. 一种石墨烯导电油墨，其特征在于：由自稳定分散石墨烯纳米材料、醇水混合溶剂和墨水粘结剂以2～4:50～100:1～2的质量比组成；
    所述自稳定分散石墨烯纳米材料由对氨基苯磺酸钠、天然鳞片石墨和醇水混合溶剂通过液相剥离法制成，所述对氨基苯磺酸钠通过π-π共轭作用、物理吸附作用及化学接枝作用于石墨烯表面。
  2. 如权利要求1所述的一种石墨烯导电油墨，其特征在于：所述天然鳞片石墨的粒径为8000目。
  3. 如权利要求1所述的一种石墨烯导电油墨，其特征在于：所述天然鳞片石墨与对氨基苯磺酸钠的质量比为1～5:1～10。
  4. 如权利要求2所述的一种石墨烯导电油墨，其特征在于：所述天然鳞片石墨与对氨基苯磺酸钠的质量比为1～2:1～2。
  5. 如权利要求1所述的一种石墨烯导电油墨，其特征在于：所述醇水混合溶剂由水和低级醇以2:3的体积比组成。
  6. 如权利要求5所述的一种石墨烯导电油墨，其特征在于：所述低级醇为乙醇、乙二醇、丙三醇、异丙醇和正丁醇中的至少一种。
  7. 如权利要求6所述的一种石墨烯导电油墨，其特征在于：所述低级醇为异丙醇。
  8. 如权利要求1所述的一种石墨烯导电油墨，其特征在于：所述墨水粘结剂为聚乙烯醇、聚乙二醇、丙烯酸树脂、环氧树脂、聚氨酯树脂、羟丙基甲基纤维素和硝化纤维素中的一种或多种。
  9. 权利要求1至8中任意一项所述的一种石墨烯导电油墨的制备方法，其特征在于：包括如下步骤：
    (1)将天然鳞片石墨、醇水混合溶剂和对氨基苯磺酸钠混合后进行超声处理，获得对氨基苯磺酸钠完全溶解的石墨分散液；
    (2)将上述石墨分散液送入研磨机进行研磨，获得研磨浆料；
    (3)将上述研磨浆料用洗涤溶剂进行离心洗涤，获得沉淀，即为所述自稳定分散石墨烯纳米材料；
    (4)将上述自稳定分散石墨烯纳米材料、粘结剂和醇水混合溶剂混合研磨，即得所述石墨烯导电油墨。
  10. 如权利要求9所述的制备方法，其特征在于：所述步骤(1)中研磨的时间为12～24h，研磨介质为粒径为2～3mm的氧化锆珠。
  11. 如权利要求9所述的制备方法，其特征在于：所述步骤(1)研磨的转速为2000rpm。
  12. 如权利要求9所述的制备方法，其特征在于：所述步骤(1)研磨时还包括对研磨装置进行冷却。
  13. 如权利要求9所述的制备方法，其特征在于：所述离心洗涤用洗涤剂为异丙醇与水组成的醇水混合溶剂，所述醇水混合溶剂中异丙醇与水的体积比为3:2。
  14. 如权利要求9所述的制备方法，其特征在于：所述步骤(4)中混合研磨的时间为2h，转速为500rpm，研磨介质为粒径为2mm的氧化锆珠。
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