US20140151608A1 - Conductive graphene-metal composite material, the production method of the same and use of the same - Google Patents

Conductive graphene-metal composite material, the production method of the same and use of the same Download PDF

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Publication number
US20140151608A1
US20140151608A1 US14/095,443 US201314095443A US2014151608A1 US 20140151608 A1 US20140151608 A1 US 20140151608A1 US 201314095443 A US201314095443 A US 201314095443A US 2014151608 A1 US2014151608 A1 US 2014151608A1
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Prior art keywords
metal
graphene
oxide
graphite oxide
treatment
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Abandoned
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US14/095,443
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Yonglian QI
Chuanxiang XU
Shi SHU
Jianshe XUE
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BOE Technology Group Co Ltd
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BOE Technology Group Co Ltd
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Assigned to BOE TECHNOLOGY GROUP CO., LTD. reassignment BOE TECHNOLOGY GROUP CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: QI, YONGLIAN, SHU, Shi, XU, CHUANXIANG, XUE, JIANSHE
Publication of US20140151608A1 publication Critical patent/US20140151608A1/en
Priority to US15/073,077 priority Critical patent/US9959946B2/en
Abandoned legal-status Critical Current

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    • 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

Definitions

  • the invention relates to a conductive graphene material, specifically, to a conductive graphene-metal composite material, the production method of the same and the use of the same.
  • ITO indiumtin oxide
  • the abrasion resistance of the ITO film is relatively poor, and at the same time the cost of indium, which is the main component of ITO, is relative high, therefore, the use of optical film having better properties, such as graphene-metal composite electrode, has become a trend.
  • the monolayer graphene is a two-dimensional structure of a closely packed atomic monolayer.
  • the specific electronic configuration thereof determines its excellent electrical property.
  • carbon atoms periodically arrange in the graphite plane in the form of six-membered ring. Each carbon atom binds three adjacent carbon atoms via 6 bonds.
  • the remaining ⁇ electrons in the Pz orbital form a ⁇ orbital in the direction perpendicular to the plane.
  • the ⁇ electrons can move in the plane of the graphene crystal, which allows the graphene to possess a good conductivity.
  • investigations indicate that transparency of a graphene electrode would not be affected when it combines in a grid style with metal having small size.
  • ITO indium tin oxide
  • An object of the invention is to overcome the disadvantages mentioned above, that is, to provide a conductive graphene-metal composite material with low price, good conductivity and superior transparency.
  • Another object of the invention is to provide a production process of said conductive graphene-metal composite material.
  • a further object of the invention is to provide said conductive graphene-metal composite material in use for manufacturing a conductive layer of a liquid crystal display.
  • the invention provides a conductive material, which is a composite of monolayer graphene nanoflakes and metal or metal oxide.
  • the conductive material can be used as an electrode material.
  • aluminium is preferably adopted as the metal
  • aluminium oxide is preferably adopted as the metal oxide.
  • the weight ratio between the monolayer graphene nanoflakes and the metal or the metal oxide is 1:50-1:600, preferably 1:100-1:400.
  • the monolayer graphene nanoflakes are prepared from graphite oxide preferably by a rapid thermal exfoliation method or a solvothermal method, preferably by a rapid thermal exfoliation method.
  • the conductive material is prepared by subjecting monolayer graphene nanoflakes and a metal or metal oxide to phase coating and mixing, preferably by an ultrasonic treatment or a mechanical agitation treatment to form a composite of monolayer graphene nanoflakes and a metal or metal oxide.
  • the invention provides a production process of a conductive material, characterized by including the steps of:
  • the step of processing the graphite oxide into a graphene suspension comprising monolayer graphene nanoflakes may include processing the graphite oxide into a graphene suspension comprising monolayer graphene nanoflakes by utilizing a rapid thermal exfoliation method or a solvothermal method.
  • the step of processing the graphite oxide into a graphene suspension comprising monolayer graphene nanoflakes may include:
  • the subjecting the graphite oxide to a heat treatment may include heat treating the graphite oxide at a temperature of 850-1300° C. for 30-50 sec.
  • the step of processing the graphite oxide into a graphene suspension comprising monolayer graphene nanoflakes may includes:
  • the weight ratio of the graphite oxide to the absolute ethanol may be 1:20-1:100.
  • the step of processing the graphene suspension and metal or metal oxide so as to provide a liquid comprising a composite may include: subjecting the graphene suspension and metal or metal oxide to an ultrasonic treatment or a mechanical agitation treatment so as to provide a liquid comprising a composite.
  • the step of processing the graphene suspension and metal or metal oxide so as to provide a liquid comprising a composite may include:
  • the solvent may be N-methyl-2-pyrrolidone.
  • the ultrasonic dispersion may include dispersion of 20-60 min under an ultrasound of 80-150 W.
  • the salt solution comprising the metal may be a solution comprising Al 3+ and SO 4 2 ⁇ .
  • the duration of the agitation treatment may last 5-10 h.
  • the weight ratio of the graphene in the graphene suspension to the metal in the salt solution comprising the metal may be 1:50-1:600.
  • the production process of a conductive graphene-metal composite material of the invention includes the steps of:
  • Said ultrasonic treatment or a mechanical agitation treatment includes:
  • the rapid thermal exfoliation method in the step 1) is: firstly, heat treating the graphite oxide at a temperature of 850-1300° C. for 30-50 sec;subsequently, adding absolute ethanol therein; then, treating it under an ultrasound of 80-150 W for 2-2.5 h, so as to provide a graphene suspension comprising monolayer graphene nanoflakes, wherein the weight ratio of the graphite oxide to the absolute ethanol is 1:20-1:100.
  • the ultrasonic treatment in the step 2) is: adding the graphene suspension into a solution of N-methyl-2-pyrrolidone, dispersing it under an ultrasound of 80-150 W for 20-60 min, adding a mixed solution comprising Al 3+ and 50 4 2 ⁇ , and stiffing it for 5-10 h.
  • the solvent is N-methyl-2-pyrrolidone.
  • the ultrasonic dispersion includes a dispersion of 20-60 min under an ultrasound of 80-150 W, the salt solution comprising the metal is a solution comprising Al 3+ and 50 4 2 ⁇ , and the stiffing lasts 5-10 h.
  • the weight ratio of the graphene in the graphene suspension to the aluminium in the salt solution comprising Al 3+ and 50 4 2 ⁇ is 1:50-1:600, preferably 1:100-1:400.
  • the high temperature treatment in the step 3) removes the solvent in the composite, and ultimately makes the monolayer graphene nanoflakes and the metal or metal oxideform a conductive network.
  • the invention adopts an ultrasonic treatment or a mechanical agitation treatment. This can ensurea good combination between the metal material and graphite active substance; and the method of mechanical agitation can avoid that the graphene disperses non-uniformly and that it is hard to form a conductive network. This can improve the electrochemical activity efficiently and reduce the resistance against the transfer of the charges efficiently.
  • the conductive graphene-metal composite material can be used as a conductive electrode used in a transparent conductive layer of a liquid crystal display, for example, a pixel electrode of an array substrate, and an electrostatic shielding layer in a color film substrate.
  • the substrate must be cleaned previously, by such as washing it with an agent, rinsing it with water directly, drying it with air knife, etc.
  • step 1) the graphene-metal composite is spin coated on the substrate by a dipping process.
  • step 2) the temperature of the high temperature treatment is 100-250° C.
  • the substrate of the liquid crystal display of the invention comprises a transparent conductive layer, which is formed of the conductive material mentioned above.
  • the liquid crystal display of the invention comprises a substrate, which comprises a transparent conductive layer, which is composed of the conductive material mentioned above.
  • the graphene-metal composite conductive material of the invention has the following advantages.
  • Themonolayer graphene nanoflakes adopted have a high conductivity and a large aspect ratio.
  • the use of ultrasonic treatment and/or the mechanical agitation treatment can ensure a good combination between the metal material and graphite active substance.
  • the method of mechanical agitation can avoid that the graphene disperses non-uniformly and that it is hard to form a conductive network. This can improve the electrochemical activity efficiently and reduce the resistance against the transfer of the charges efficiently.
  • the cost of the current process for sputtering ITO with a sputter can be reduced, and the costs of the processes and facilities can be reduced, therefore, this material can be used for replacing the ITO conductive layer of the liquid crystal display.
  • FIG. 1 is a flow chart of the production process of the graphene-metal composite electrode of the invention.
  • the conductive graphene-metal composite material of the invention is a composite of monolayer graphene nanoflakes and metal or metal oxide.
  • the metal or metal oxide can be aluminium and aluminium oxide, respectively.
  • As the metal a metal that is appropriate in terms of conductivity and price or cost, preferably aluminium, can be adopted.
  • Other metal also can be used, such as Ag.
  • the conductive material is prepared by subjecting monolayer graphene nanoflakes and a metal or metal oxide to a phase coating and mixing by an ultrasonic treatment or a mechanical agitation treatment.
  • the weight ratio between the monolayer graphene nanoflakes and aluminium or aluminium oxide is 1:50-1:600, preferably 1:100-1:400.
  • the monolayer graphene nanoflakes are prepared from graphite oxide by a rapid thermal exfoliation method or a solvothermal method, preferably by a rapid thermal exfoliation method.
  • Monolayer graphene nanoflakes thus obtained have high conductivity and large aspect ratio.
  • the production process of the conductive graphene-metal composite material of the invention includes steps of:
  • the graphene suspension into a solution of N-methyl-2-pyrrolidone, dispersing it under an ultrasonic wave of 80-150 W for 20-60 min, adding a mixed solution (the solution can be a salt solution or alkali solution comprising the metal) comprising Al 3+ and SO 4 2 ⁇ , and stirring it under a rate of the agitation of 500-1000 rpm for 5-10 h, wherein it is desired that the amount of the N-methyl-2-pyrrolidone added ensures the good dispersion of the graphene, and preferably the volume ratio of the graphene suspension to the solution of N-methyl-2-pyrrolidone is 1:1-1:5;
  • the weight ratio of the graphene in the graphene suspension to the aluminium in the mixed solution is 1:50-1:600;
  • the rate of the agitation is 500-1000 rpm.
  • the conductive graphene-metal composite material of the invention can be used as a conductive electrode used in a transparent conductive layer of a liquid crystal display, for example, a pixel electrode of an array substrate, and an electrostatic shielding layer in a color film substrate.
  • An embodiment of the present invention further provides a liquid crystal display device comprising a conductive film, wherein the conductive film is formed of the conductive material according to any embodiment of the invention.
  • FIG. 1 a flow chart of the production process of the graphene-metal composite electrode of the invention is provided.
  • the production process of the graphene-metal composite electrode was as followings.
  • N-methyl-2-pyrrolidone N-methyl-2-pyrrolidone, and then dispersed for 30 min by being placed in an ultrasonic cleaner at 100 W.
  • 15 L mixed solution comprising Al 3+ and SO 4 2 ⁇ (concentration: 10 mol/L) was added therein.
  • the mixture was magnetically stirred (stirring rate: 500 rpm) for 5 h to provide a graphene-metal composite.
  • the graphene-metal composite electrode (a composite of monolayer graphene nanoflakes and aluminium oxide, weight ratio: 1:160) was produced on the glass substrate by a high temperature treatment at 300° C. under the protection of an inert gas. It could serve as an alternative electrode of the indium tin oxide (ITO) conductive layer, i.e. graphene-metallic aluminium composite electrode.
  • ITO indium tin oxide
  • the graphene-metal composite electrode had improved transparency and conductivity. On the premise of good properties, the costs of processes and facilities were reduced.
  • the resistances of the transparent conductive layer thin films formed of the graphene-metal composite material of the invention were tested. The comparison between the results of them and an ITO thin film was shown in the table below.
  • the transparent conductive thin films obtained in the present invention had excellent conductivity and transparency.

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US14/095,443 2012-12-03 2013-12-03 Conductive graphene-metal composite material, the production method of the same and use of the same Abandoned US20140151608A1 (en)

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US10527904B2 (en) * 2015-08-10 2020-01-07 Boe Technology Group Co., Ltd. Display device and apparatus, liquid metal material, related fabricating molds, methods, and apparatus
CN113753870A (zh) * 2021-09-30 2021-12-07 海南大学 一种锂离子电池用GeP纳米片负极及其超声波辅助快速剥离制备方法

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CN103926755B (zh) * 2013-12-30 2017-08-25 厦门天马微电子有限公司 一种显示器及其制作方法
CN103741094A (zh) * 2014-01-22 2014-04-23 武汉理工大学 石墨烯复合导电氧化物靶材及其透明导电薄膜的制备方法
CN104880844A (zh) * 2015-05-22 2015-09-02 重庆捷尔士显示技术有限公司 一种新型液晶显示器及制作方法
CN107731353B (zh) * 2017-10-11 2019-05-24 中节能(唐山)环保装备有限公司 石墨烯金属氧化物电极材料的制备方法
CN110190070B (zh) * 2019-05-29 2021-11-02 深圳市华星光电半导体显示技术有限公司 三维多孔结构复合体材料及制备方法、阵列基板
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CN113753870A (zh) * 2021-09-30 2021-12-07 海南大学 一种锂离子电池用GeP纳米片负极及其超声波辅助快速剥离制备方法

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US9959946B2 (en) 2018-05-01
US20160196890A1 (en) 2016-07-07
CN103000245A (zh) 2013-03-27
CN103000245B (zh) 2015-09-23

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