WO2018133531A1 - Flexible transparent electrode, and manufacturing method and application thereof - Google Patents

Flexible transparent electrode, and manufacturing method and application thereof Download PDF

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Publication number
WO2018133531A1
WO2018133531A1 PCT/CN2017/112410 CN2017112410W WO2018133531A1 WO 2018133531 A1 WO2018133531 A1 WO 2018133531A1 CN 2017112410 W CN2017112410 W CN 2017112410W WO 2018133531 A1 WO2018133531 A1 WO 2018133531A1
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transparent electrode
flexible transparent
plant
flexible
flexible substrate
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PCT/CN2017/112410
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French (fr)
Chinese (zh)
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包磊
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深圳市前海未来无限投资管理有限公司
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    • 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
    • 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

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  • the invention belongs to the technical field of electronic materials, and in particular relates to a flexible transparent electrode and a preparation method and application thereof.
  • ITO Indium Tin Oxide
  • Sn 2 O 3 Sn 2 O 3
  • ITO Indium in ITO is a scarce element. It is increasingly reduced in content on the earth, and the price is gradually rising. It does not meet the demands of low-cost mass production.
  • ITO itself is hard and brittle, not easily deformed, and is not suitable for a new generation of electronic products. The requirements for bending and stretching are not suitable for use in smart wear, especially for electronic skin.
  • Silver is a good conductor of electricity and heat and has excellent ductility. When reduced to nanometer size, silver nanostructures exhibit excellent optoelectronic and mechanical properties.
  • the film forming technology of silver wire there have been many kinds, such as ordinary spin coating, screen printing, precision monomolecular film arrangement, etc. It is widely used in the production of flexible electrodes.
  • the silver nanowires developed by the current process have a small aspect ratio and limit its photoelectric properties.
  • the existing film forming techniques have certain disadvantages, such as the affinity of the silver wire and the substrate for spin coating. Single-molecule film formation involves many harmful chemical agents, which are not conducive to environmental and physical and mental health. These defects are difficult to achieve low-cost green mass production.
  • a transparent electrode is prepared by using the veins.
  • the specific method is as follows: firstly, the leaf vein template is prepared, the fresh leaves are soaked by the alkali solution, and the brush is beaten, and the leaf veins are removed to leave the intact veins.
  • the vein template is obtained; the metal film is deposited, and a dense metal film is deposited on the vein template to prepare a vein metal electrode; then the outer layer is coated with polydimethylsiloxane PDMS, and the leaf vein transparent conductive electrode is packaged and packaged by PDMS.
  • a leaf-shaped transparent conductive electrode is obtained.
  • the transparent electrode prepared by the method successfully utilizes the structure of the veins on the veins, and makes the electrodes have good electrical conductivity, light transmittance and flexibility, the template can not be removed, which causes visible obstacles to the naked eye, which not only affects The conductivity of the electrode makes it have a large electrical resistance and affects the transparency, which is not suitable for use in real technology.
  • the object of the present invention is to overcome the above-mentioned deficiencies of the prior art, and to provide a flexible transparent electrode and a preparation method thereof, so as to solve the technical problem that the existing transparent flexible electrode has poor conductivity and low transparency.
  • Another object of the present invention is to provide an electronic skin that solves the technical problem that the conductivity of the electrode contained in the existing electronic skin is not ideal, and the transparency is not high, thereby affecting the performance and use effect of the electronic skin.
  • a flexible transparent electrode in one aspect of the invention, includes a flexible substrate having a metal conductive layer bonded thereto, wherein the metal conductive layer is in a plant vein pattern, and the metal conductive material is a silver nanowire.
  • a method of making a flexible transparent electrode comprises the following steps:
  • Pressure is applied in the direction of the flexible substrate on the other surface of the plant vein such that the silver nanowires form the plant vein pattern conductive layer on the surface of the flexible substrate.
  • an electronic skin comprises the flexible transparent electrode of the present invention or a flexible transparent electrode prepared by the preparation method of the present invention.
  • the flexible transparent electrode of the present invention combines the silver nanowire conductive layer of the biomimetic plant vein pattern on the surface of the flexible substrate. Since the vein has a natural perfect vein structure and morphology, the flexible transparent electrode of the present invention has Excellent electrical conductivity and light transmission properties, as well as excellent flexibility and mechanical stability.
  • the method for preparing the flexible transparent electrode of the invention adopts the vein-assisted dry transfer method, that is, the plant veins are used as a template, and the silver nanowires form a conductive layer of the bionic plant vein pattern on the surface of the flexible substrate, because the veins have a natural perfect vein structure and shape.
  • the appearance makes the prepared flexible transparent electrode have excellent electrical conductivity and excellent flexibility.
  • the preparation method of the invention avoids coating the veins in the conductive layer, thereby reducing the internal resistance of the conductive layer and ensuring the light transmittance thereof.
  • the preparation method of the invention avoids the use of harmful chemical reagents, ensures environmental protection and safety during the preparation process, and has simple preparation process and high speed, and can be carried out only at normal temperature, and utilizes abundant leaf vein templates in nature. Low cost, suitable for green and low-cost mass production.
  • the electronic skin of the present invention is sensitive to the electronic skin of the present invention because it contains the flexible transparent electrode of the present invention or the flexible transparent electrode prepared by the preparation method of the present invention, and the biofilming effect is excellent due to the high transparency of the electrode.
  • FIG. 1 is a schematic structural view of a flexible transparent electrode according to an embodiment of the present invention.
  • FIG. 2 is a scanning electron micrograph of a 50 nm-diameter and 2 cm-length silver nanowire contained in a flexible transparent metal conductive layer according to an embodiment of the present invention; wherein, FIG. 2a is a 50 nm scanning electron micrograph of the size silver nanowire; FIG. 2b is a silver of the size Nanowire 30nm scanning electron micrograph;
  • FIG. 3 is a flow chart of a method for preparing a flexible transparent electrode according to an embodiment of the present invention.
  • Figure 4 is a diagram showing the leaf vein of a plant according to an embodiment of the present invention.
  • inventions of the present invention provide a flexible transparent electrode having high conductivity and transparency.
  • the flexible transparent electrode as shown in FIG. 1, comprises a flexible substrate 1 on the surface of which a metal conductive layer 2 is bonded.
  • the metal conductive layer 2 has a plant vein pattern, and the metal conductive material is a silver nanowire.
  • the metal conductor layer 2 is formed by the silver veins of the plant vein pattern, and the vein formed by the plant in the long-term natural evolution process has its own specific perfect vein structure and morphology, so that the metal conductor layer 2 is blocked. Small, with excellent electrical and optical properties and elasticity. When combined with the flexible substrate 1, it imparts excellent electrical conductivity, light transmission property and flexibility, and mechanical properties to the flexible transparent electrode.
  • the silver nanowire plant vein pattern in the metal conductive layer 2 contained in the flexible transparent electrode is a plant vein pattern such as sweet-scented osmanthus, poplar, magnolia or maple.
  • the silver nanowires are arranged into the specific vein pattern of the plant, and the natural vein structure and morphology of the plant veins, that is, the silver nanowires are interconnected in a perfect vein structure to form a specific network, effectively imparting metal conduction.
  • the excellent electrical conductivity of the layer 2 and the mechanical properties such as toughness ensure the electrical conductivity and flexible mechanical stability of the flexible transparent electrode.
  • the conventional leaf vein pattern is not used, the transparency of the conductive layer can only be determined by the gap between the nanowire and the nano silver wire, but the above is done.
  • the metal conductive layer 2 is composed of a pure silver nanowire from the vein pattern of the nanowire plant which does not contain the plant vein body, that is, the silver nanowire plant vein pattern. Therefore, the metal conductor layer 2 of the vein pattern of the silver nanowire plant has low internal resistance, excellent electrical conductivity, and high transparency, thereby improving the application range thereof, such as particularly improving the application effect in the electronic skin.
  • the silver nanowires constituting the vein pattern of the plant are 20-50 nm in diameter and 200 ⁇ m-2 cm in length.
  • the silver nanowires are 50 nm in diameter and 2 cm in length; or 20 nm in diameter and 200 um in length.
  • the scanning electron micrograph of the silver nanowire with a diameter of 50 nm and a length of 2 cm is shown in FIG. 2a and FIG. 2b.
  • the silver nanowire has a long length and a nanometer diameter, and has a good gap between adjacent silver nanowires, thereby improving the gap. transparency.
  • the silver nanowires of this length are selected and formed into a specific perfect vein structure and morphology of the plant veins, which effectively improves the electrical conductivity of the metal conductive layer 2 and the toughness and stability of the perfect vein structure, and improves the transparency.
  • the flexible substrate 1 contained in the flexible transparent electrode in each of the above embodiments may be selected from an organic resin matrix suitable for electronic skin such as ethylene phthalate (PET) or polydimethylsiloxane (PDMS).
  • PET ethylene phthalate
  • PDMS polydimethylsiloxane
  • Other properties of the flexible substrate 1, such as thickness flexibility, can be flexibly selected and controlled depending on the needs of the particular application, such as the performance of the electronic skin.
  • Any substrate capable of effectively bonding the metal conductive layer 2 of the above specific pattern and conforming to the transparency requirements and flexibility requirements is within the scope of the present disclosure.
  • a polydimethylsiloxane (PDMS) substrate can be obtained as follows:
  • the PDMS of the product SYLGARD 184 of Dow Corning, and the basic component and the curing agent are mixed in a weight ratio of 10:1, stirred for 10 minutes, left to stand for 0.5-1 hour to remove bubbles, or a vacuum system is used. About 10 minutes.
  • the sample obtained by spin coating was heated on a hot plate at a temperature of 90-150 ° C and a curing time of 30-60 min. PDMS is fully cured and then removed from PET The substrate was peeled off to obtain a flexible, elastically stretchable flexible substrate.
  • the flexible transparent electrode in each of the above embodiments was tested to have a sheet resistance of about 1-5 ⁇ /sq and a transparency of 82% to 90%.
  • the metal conductive layer 2 of the flexible transparent electrode of the embodiment of the present invention is a silver nanowire conductive layer of a bionic plant vein pattern. Since the vein has a natural perfect vein structure and morphology, the flexible transparent electrode of the embodiment of the present invention has Excellent electrical conductivity and light transmission properties, as well as excellent flexibility and mechanical stability.
  • embodiments of the present invention also provide a method of preparing the flexible transparent electrode described above.
  • the preparation method flow is shown in FIG. 3, and the flexible transparent electrode is also shown in FIG. 1 and includes the following steps:
  • a silver nanowire is attached to one side of the filter membrane: the dispersion of the silver nanowire 21 is filtered by the filter membrane 3, so that the silver nanowire 21 is attached to a surface of the filter membrane;
  • the plant veins, the filter membrane with the silver nanowires and the flexible substrate are sequentially attached: the filter membrane 3 is attached to the surface of the flexible substrate 1 and the filter with the silver nanowires 21 attached thereto The surface of the membrane 3 is adhered to the surface of the flexible substrate 1, and then the prepared leaf veins of the removed mesophyll 4 are stacked on the other surface of the filter membrane 3;
  • the filtration method can be filtered by conventional filtration such as vacuum filtration to improve filtration efficiency.
  • the silver nanowire 21 has a dispersion concentration of 1-5 mg/ml.
  • the dispersion of the silver nanowires 21 may be obtained by fractionally dispersing the silver nanowires 21 into absolute ethanol to obtain a uniform dispersion by ultrasonication.
  • the silver nanowire 21 has a diameter of 20-50 nm and a length of 200 ⁇ m-2 cm as described in the flexible transparent electrode above.
  • the silver nanowire 21 The diameter is 50 nm, the length is 2 cm; or the diameter is 20 nm, the length is 200 ⁇ m, and the like.
  • the silver nanowire 21 of the size is prepared as follows:
  • a vanadium foil is placed in the AgNO 3 solution to carry out a displacement reaction to form a silver nanowire 21, and the heating temperature is controlled to be between 20 and 100 degrees for a period of 2 to 5 hours.
  • the concentration of the AgNO 3 solution is preferably 0.01-0.1 mg/ml, and the amount thereof may be determined according to the amount of the silver wire, such as, but not limited to, 10 ml.
  • the method can effectively obtain silver nanowires 21 of long length and direct nanometer order, such as obtaining silver nanowires 21 with a diameter of 20-50 nm and a length of 200 ⁇ m-2 cm of silver nanowires.
  • the silver nanowires 21 of this length can be interwoven with each other, effectively ensuring the electrical conductivity of the conductive layer 2.
  • the thickness of the silver nanowires 21 attached to the surface of the filter membrane 3 is controlled to be from 100 nm to 500 nm.
  • the filter membrane is a commercially available acetate filter membrane having a pore size of 0.02 [mu]m.
  • the quality of the plant vein pattern conductive layer finally formed on the surface of the flexible substrate 1 is improved.
  • the flexible substrate 1 may be the flexible substrate 1 as described in the flexible transparent electrode above, and the details are not described herein for the sake of space saving.
  • the plant vein 4 and the filter membrane 3 with the silver nanowire 21 are attached to the flexible substrate 1 to form a three-layer structure in which the plant vein 4, the filter membrane 3 and the flexible substrate 1 are sequentially laminated, wherein the layer formed by the silver nanowire 21 The structure is disposed between the filter membrane 3 and the flexible substrate 1.
  • the plant vein 4 is shown in Fig. 4.
  • the raw plant leaves of the plant vein 4 may be plant leaves such as sweet-scented osmanthus, poplar, magnolia or maple
  • the plant veins 4 are corresponding plant veins such as sweet-scented osmanthus, poplar, magnolia or maple.
  • the plant vein 4 can be prepared as follows:
  • the leaves are removed into the alkali solution, heated to 90-120 ° C, and taken out for 0.5-2 hours, and the corroded mesophyll is removed, washed and dried.
  • the plant mesophyll can be effectively removed, and the intact plant veins are retained, that is, the complete perfect network structure of the intact plant veins is retained.
  • step S03 under the action of applying pressure along the flexible substrate 1, due to planting The vein template 4 or the corresponding action and the filter film, so that the silver nanowire 21 is in contact with the surface of the flexible substrate 1, thereby transferring the choroidal structure pattern of the plant vein 4 with the silver nanowire 21 as a medium to transfer the surface of the flexible substrate 1 so that silver
  • the nanowires 21 form a specific perfect vein network structure pattern such as that of the plant veins 4 on the surface of the flexible substrate 1, forming a plant vein pattern conductive layer 2.
  • the pressure is about 5-15 MPa.
  • step S03 After the above step S03 is performed, it is a matter of course to include the step S04 shown in FIG. 3: that is, the removal of the plant vein 4 template and the filter membrane 3.
  • the above-mentioned flexible transparent electrode preparation method adopts the vein-assisted dry transfer method, that is, the plant vein 3 is used as a template, and the silver nanowire 21 forms a bionic plant vein pattern conductive layer 2 on the surface of the flexible substrate 1, since the vein 3 has natural
  • the perfect choroid structure and morphology make the prepared flexible transparent electrode have excellent electrical conductivity and excellent flexibility.
  • the above preparation method avoids coating the veins 3 in the conductive layer 2, which reduces the internal resistance of the conductive layer 2 and ensures its light transmittance.
  • the above preparation method avoids the use of harmful chemical reagents, ensures environmental protection and safety during the preparation process, and has simple preparation process and high speed, and can be carried out only at normal temperature, and utilizes rich leaf vein template in nature, and costs Low cost, suitable for green and low-cost mass production.
  • the embodiment of the invention further provides an electronic skin.
  • the electronic skin should be understood to include components that the electronic skin should contain, such as a bionic skin body and an electrode, wherein the electrode is a flexible transparent electrode as described in the above embodiments of the invention or as described in the above embodiments of the invention.
  • Preparation Method The obtained flexible transparent electrode was prepared. Since the electronic skin of the embodiment of the present invention contains the flexible transparent electrode of the embodiment of the present invention, the electronic skin sensing of the embodiment of the present invention is sensitive, and the biomimetic effect is excellent due to the high transparency of the electrode.
  • the above flexible transparent electrode can also be used for a touch screen of a mobile phone, a screen of an OLED, or the like.
  • the present invention provides a flexible transparent electrode having a structure as shown in FIG. 1, comprising a PET flexible substrate 1 on the surface of which a metal conductive layer 2 is bonded.
  • the metal conductive layer 2 is a vein pattern of a osmanthus leaf plant
  • the metal conductive material is a silver nanowire
  • the silver nanowire has a diameter of 50 nm and a length of 2 cm.
  • the preparation method is as follows, referring to the process flow described in FIG. 3:
  • Step S11 taking 3 ml of the silver nanowire dispersion into the vacuum suction device in which the fiber filter is placed 2 times, so that the silver nanowire adheres to a surface of the filter;
  • the preparation method of the silver nanowire dispersion liquid 1 mg of a silver nanowire (a diameter of 50 nm, a length of 2 cm, as shown in FIG. 2) with a large aspect ratio is dissolved in 50 ml of absolute ethanol and dispersed by ultrasonic 1 ⁇ 2 minutes or magnetic stirring for 10 minutes to obtain a uniform silver wire dispersion to obtain a silver nanowire dispersion having a concentration of 0.02 mg/ml;
  • Step S12 quickly pick up the filter of the silver nanowire in step S11 and contact it with the flexible substrate PET (polyethylene terephthalate), and then stack the prepared leaf veins of the removed mesophyll On the other surface of the filter membrane;
  • PET polyethylene terephthalate
  • the preparation method of the prepared leaf vein for removing the mesophyll is as follows:
  • Step S13 applying a pressure of 10-15 MPa in the direction of the flexible substrate on the other surface of the plant vein, such that the silver nanowire is transferred to the surface of the flexible substrate, and the plant vein is formed on the surface of the flexible substrate.
  • Patterned conductive layer
  • Step S14 After 30 s, the plant veins and the filter are removed to obtain a flexible transparent electrode of the present embodiment.
  • the present invention provides a flexible transparent electrode having a structure as shown in FIG. 1, comprising a PET flexible substrate 1 on the surface of which a metal conductive layer 2 is bonded.
  • the metal conductive layer 2 has a vein pattern of poplar plants, and the metal conductive material is a silver nanowire, and the silver nanowire has a diameter of 20 nm and a length of 200 ⁇ m.
  • the preparation method is as follows, referring to the process flow described in FIG. 3:
  • Step S21 Refer to step 11 in Embodiment 1, except that the silver nanowire has a diameter of 20 nm and a length of 200 ⁇ m;
  • Step S22 Refer to step 12 in Embodiment 1;
  • Step S23 refer to step 13 in Embodiment 1;
  • Step S24 Refer to step 14 in Embodiment 1.
  • the present invention provides a flexible transparent electrode having a structure as shown in FIG. 1, comprising a PDMS flexible substrate 1 having a metal conductive layer 2 bonded to the surface of the flexible substrate 1.
  • the metal conductive layer 2 is in the vein pattern of the magnolia plant, and the metal conductive material is a silver nanowire, and the silver nanowire has a diameter of 50 nm and a length of 2 cm.
  • the preparation method is as follows, referring to the process flow described in FIG. 3:
  • Step S31 refer to step 11 in Embodiment 1;
  • Step S32 Refer to step 12 in Embodiment 1;
  • Step S33 Refer to step 13 in Embodiment 1;
  • Step S34 Refer to step 14 in Embodiment 1.
  • the present invention provides a flexible transparent electrode having a structure as shown in FIG. 1, comprising a PDMS flexible substrate 1 having a metal conductive layer 2 bonded to the surface of the flexible substrate 1.
  • the metal conductive layer 2 is The maple plant has a vein pattern, and the metal conductor is a silver nanowire.
  • the silver nanowire has a diameter of 50 nm and a length of 2 cm.
  • the preparation method is as follows, referring to the process flow described in FIG. 3:
  • Step S41 refer to step 11 in Embodiment 1,
  • Step S42 Refer to step 12 in Example 1, except that the lye used for preparing plant veins is a concentration of 0.1-0.3 g/mL potassium hydroxide;
  • Step S43 Refer to step 13 in Embodiment 1;
  • Step S44 Refer to step 14 in Embodiment 1.

Abstract

A flexible transparent electrode, a manufacturing method thereof, and an electronic skin. The flexible transparent electrode comprises a flexible substrate (1) combined at a surface thereof with a metal conductive material layer (2). The metal conductive material layer (2) comprises a plant vein pattern. A metal conductive material is a silver nanowire. The flexible transparent electrode has favorable electrical conductivity and light transmission performance, and favorable flexibility and mechanical stability. The manufacturing method thereof ensures stable performance of a manufactured flexible transparent electrode, ensures safety and environmental friendliness during a manufacturing process, is simple in manufacturing technique and fast in speed, can be used in a room temperature, utilizes various leaf vein patterns in the nature, is low in cost and suitable for environmentally friendly low-cost mass production. The electronic skin comprising the flexible transparent electrode is quick in response and can achieve a favorable bionic effect resulting from high transparency of the electrode.

Description

柔性透明电极及其制备方法与应用Flexible transparent electrode and preparation method and application thereof 技术领域Technical field
本发明属于电子材料技术领域，具体的是涉及一种柔性透明电极及其制备方法与应用。The invention belongs to the technical field of electronic materials, and in particular relates to a flexible transparent electrode and a preparation method and application thereof.
背景技术Background technique
金属氧化物，尤其是ITO(Indium Tin Oxide铟锡氧化物)是目前应用最为广泛的透明电极材料，常常应用于平板显示，太阳能电池，有机发光二极管等一系列相关技术中作为一种N型氧化物半导体。ITO用作电极时的透光率和导电性往往由In2O3与Sn2O3的比例来调控，其工艺制备则一般采用真空蒸镀。Metal oxides, especially ITO (Indium Tin Oxide), are the most widely used transparent electrode materials, and are often used as an N-type oxidation in a series of related technologies such as flat panel display, solar cells, and organic light-emitting diodes. Semiconductor. The light transmittance and conductivity when ITO is used as an electrode are often controlled by the ratio of In 2 O 3 to Sn 2 O 3 , and the process is generally carried out by vacuum evaporation.
ITO中的铟属于稀缺元素，在地球上含量日益减少，价格逐步攀升，不符合低成本量产的诉求，此外，ITO本身性质硬脆易碎，不易变形，不适合新一代电子产品在柔软可弯曲和拉伸方面的诉求，故不适合应用于智能穿戴中，尤其是电子皮肤。Indium in ITO is a scarce element. It is increasingly reduced in content on the earth, and the price is gradually rising. It does not meet the demands of low-cost mass production. In addition, ITO itself is hard and brittle, not easily deformed, and is not suitable for a new generation of electronic products. The requirements for bending and stretching are not suitable for use in smart wear, especially for electronic skin.
纳米技术的兴起为透明电极的发展开拓了一个全新的方向，金属纳米线、碳纳米管和石墨烯的出现引领了一波柔性电极的浪潮。这些材料所表现出来的优异的导电性和杰出的光透射率以及良好的机械性能自然而然地成为传统导电电极的替代物。但是该纳米材料如石墨烯，尤其是用CVD法合成的石墨烯缺陷较多，接触电阻大，同时量产技术尚未成熟；碳纳米管的纯度，如手性，催化剂的存在等大大地限制了其在这方面的应用。The rise of nanotechnology has opened up a new direction for the development of transparent electrodes. The emergence of metal nanowires, carbon nanotubes and graphene has led to a wave of flexible electrodes. The excellent electrical conductivity and excellent light transmission and good mechanical properties exhibited by these materials naturally become a substitute for conventional conductive electrodes. However, the nanomaterials such as graphene, especially graphene synthesized by CVD method, have many defects, large contact resistance, and mass production technology is not yet mature; the purity of carbon nanotubes, such as chirality, presence of catalyst, etc., is greatly limited. Its application in this regard.
银是电和热的良导体，拥有极好的延展性，当缩小到纳米尺寸时，银线纳米结构可展现出优异的光电性能和机械性能。而关于银线的成膜技术，已经涌现了很多种，如普通的旋涂，丝网印刷，精密的单分子膜排布等，均已 被广泛地应用在柔性电极的生产中。但是目前工艺研制出的银纳米线具有较小的长径比，限制它的光电性能，此外，现有的成膜技术都有一定的缺点，如旋涂需要银线和基底的亲和性，单分子成膜则会涉及很多有害化学试剂，不利于环境和身心健康等，这些缺陷很难实现低成本绿色量产。Silver is a good conductor of electricity and heat and has excellent ductility. When reduced to nanometer size, silver nanostructures exhibit excellent optoelectronic and mechanical properties. As for the film forming technology of silver wire, there have been many kinds, such as ordinary spin coating, screen printing, precision monomolecular film arrangement, etc. It is widely used in the production of flexible electrodes. However, the silver nanowires developed by the current process have a small aspect ratio and limit its photoelectric properties. In addition, the existing film forming techniques have certain disadvantages, such as the affinity of the silver wire and the substrate for spin coating. Single-molecule film formation involves many harmful chemical agents, which are not conducive to environmental and physical and mental health. These defects are difficult to achieve low-cost green mass production.
基于现有制备电极的不足，出现了采用叶脉制备一种透明电极，具体方法是：先制作叶脉模板，将新鲜树叶经碱液浸泡、毛刷敲打后，去除叶肉留下完整叶脉，经压制后得到叶脉模板；再金属薄膜沉积，在叶脉模板上沉积致密的金属薄膜，制得叶脉金属电极；然后外层包裹聚二甲基硅氧烷PDMS，将叶脉透明导电电极利用PDMS进行包裹封装，制备获得树叶状透明导电电极。该方法制备的透明电极虽然叶脉上镀银虽然成功地利用了叶脉的结构，并使得电极具有很好的导电性和透光性以及柔性，但无法去除叶脉这个模板致使肉眼可见障碍，不仅影响了电极的导电性，使得其电阻大，而且影响了透明性，不适合应用于现实技术当中。Based on the shortcomings of the existing electrode preparation, a transparent electrode is prepared by using the veins. The specific method is as follows: firstly, the leaf vein template is prepared, the fresh leaves are soaked by the alkali solution, and the brush is beaten, and the leaf veins are removed to leave the intact veins. The vein template is obtained; the metal film is deposited, and a dense metal film is deposited on the vein template to prepare a vein metal electrode; then the outer layer is coated with polydimethylsiloxane PDMS, and the leaf vein transparent conductive electrode is packaged and packaged by PDMS. A leaf-shaped transparent conductive electrode is obtained. Although the transparent electrode prepared by the method successfully utilizes the structure of the veins on the veins, and makes the electrodes have good electrical conductivity, light transmittance and flexibility, the template can not be removed, which causes visible obstacles to the naked eye, which not only affects The conductivity of the electrode makes it have a large electrical resistance and affects the transparency, which is not suitable for use in real technology.
发明内容Summary of the invention
本发明的目的在于克服现有技术的上述不足，提供一种柔性透明电极及其制备方法，以解决现有透明柔性电极导电性能不理想，且透明度不高的技术问题。The object of the present invention is to overcome the above-mentioned deficiencies of the prior art, and to provide a flexible transparent electrode and a preparation method thereof, so as to solve the technical problem that the existing transparent flexible electrode has poor conductivity and low transparency.
本发明的另一目的在于提供一种电子皮肤，以解决现有电子皮肤所含的电极导电性不理想，透明度不高从而影响电子皮肤的性能和使用效果的技术问题。Another object of the present invention is to provide an electronic skin that solves the technical problem that the conductivity of the electrode contained in the existing electronic skin is not ideal, and the transparency is not high, thereby affecting the performance and use effect of the electronic skin.
为了实现上述发明目的，本发明的一方面，提供了一种柔性透明电极。所述柔性透明电极包括柔性基底，在所述柔性衬底表面结合有金属导电物层，其中，所述金属导电物层呈植物叶脉状图案，且金属导电物为银纳米线。In order to achieve the above object of the invention, in one aspect of the invention, a flexible transparent electrode is provided. The flexible transparent electrode includes a flexible substrate having a metal conductive layer bonded thereto, wherein the metal conductive layer is in a plant vein pattern, and the metal conductive material is a silver nanowire.
本发明的另一方面，提供了一种柔性透明电极的制备方法。所述制备方法包括如下步骤： In another aspect of the invention, a method of making a flexible transparent electrode is provided. The preparation method comprises the following steps:
将银纳米线的分散液用滤膜过滤，使得所述银纳米线附着在所述滤膜的一表面；Dissolving the dispersion of the silver nanowires with a filter membrane, so that the silver nanowires are attached to a surface of the filter membrane;
将所述滤膜贴合在柔性基底表面上，并使得附有所述银纳米线的所述滤膜表面与所述柔性基底表面贴合，然后将制备的除去叶肉的植物叶脉叠设在所述滤膜的另一表面上；Laminating the filter membrane on the surface of the flexible substrate, and bonding the surface of the filter membrane with the silver nanowires to the surface of the flexible substrate, and then stacking the prepared leaf veins of the removed mesophyll On the other surface of the filter membrane;
在所述植物叶脉另一表面沿所述柔性基底方向施加压力，使得所述银纳米线在所述柔性基底表面形成所述植物叶脉状图案导电层。Pressure is applied in the direction of the flexible substrate on the other surface of the plant vein such that the silver nanowires form the plant vein pattern conductive layer on the surface of the flexible substrate.
本发明的又一方面，提供了一种电子皮肤。所述电子皮肤包括本发明所述的柔性透明电极或由本发明制备方法制备获得的柔性透明电极。In yet another aspect of the invention, an electronic skin is provided. The electronic skin comprises the flexible transparent electrode of the present invention or a flexible transparent electrode prepared by the preparation method of the present invention.
与现有技术相比，本发明柔性透明电极在柔性衬底表面结合仿生植物叶脉状图案的银纳米线导电层，由于叶脉具有天然的完美脉络结构和形貌，使得本发明柔性透明电极在具有优异的导电性能和透光性能的同时，还具有优异的柔性，机械稳定性。Compared with the prior art, the flexible transparent electrode of the present invention combines the silver nanowire conductive layer of the biomimetic plant vein pattern on the surface of the flexible substrate. Since the vein has a natural perfect vein structure and morphology, the flexible transparent electrode of the present invention has Excellent electrical conductivity and light transmission properties, as well as excellent flexibility and mechanical stability.
本发明柔性透明电极制备方法采用叶脉辅助干法转印法即是以植物叶脉为模板，将银纳米线在柔性基底表面形成仿生植物叶脉状图案导电层，由于叶脉具有天然的完美脉络结构和形貌，使得制备的柔性透明电极具有优异的导电性能和优异的柔性。本发明制备方法避免了将叶脉包覆于导电层中，这样降低了导电层的内阻，保证了其透光性。另外，本发明制备方法避免了有害化学试剂的使用，保证了其制备过程中的环保安全，而且制备工艺简单，速度快，只需在常温下进行即可，利用自然界里丰富的树叶叶脉模板，成本低廉，适合绿色低成本量产。The method for preparing the flexible transparent electrode of the invention adopts the vein-assisted dry transfer method, that is, the plant veins are used as a template, and the silver nanowires form a conductive layer of the bionic plant vein pattern on the surface of the flexible substrate, because the veins have a natural perfect vein structure and shape. The appearance makes the prepared flexible transparent electrode have excellent electrical conductivity and excellent flexibility. The preparation method of the invention avoids coating the veins in the conductive layer, thereby reducing the internal resistance of the conductive layer and ensuring the light transmittance thereof. In addition, the preparation method of the invention avoids the use of harmful chemical reagents, ensures environmental protection and safety during the preparation process, and has simple preparation process and high speed, and can be carried out only at normal temperature, and utilizes abundant leaf vein templates in nature. Low cost, suitable for green and low-cost mass production.
本发明电子皮肤由于含有本发明柔性透明电极或本发明制备方法制备的柔性透明电极，这样，本发明电子皮肤感应灵敏，而且由于电极的透明度高，其生物仿生效果优异。The electronic skin of the present invention is sensitive to the electronic skin of the present invention because it contains the flexible transparent electrode of the present invention or the flexible transparent electrode prepared by the preparation method of the present invention, and the biofilming effect is excellent due to the high transparency of the electrode.
附图说明 DRAWINGS
图1为本发明实施例柔性透明电极结构示意图；1 is a schematic structural view of a flexible transparent electrode according to an embodiment of the present invention;
图2为本发明实施例柔性透明的金属导电层中所含直径50nm、长度2cm银纳米线的扫描电镜图；其中，图2a为该尺寸银纳米线50nm扫描电镜图；图2b为该尺寸银纳米线30nm扫描电镜图；2 is a scanning electron micrograph of a 50 nm-diameter and 2 cm-length silver nanowire contained in a flexible transparent metal conductive layer according to an embodiment of the present invention; wherein, FIG. 2a is a 50 nm scanning electron micrograph of the size silver nanowire; FIG. 2b is a silver of the size Nanowire 30nm scanning electron micrograph;
图3为本发明实施例柔性透明电极制备方法流程图；3 is a flow chart of a method for preparing a flexible transparent electrode according to an embodiment of the present invention;
图4为本发明实施例植物叶脉图。Figure 4 is a diagram showing the leaf vein of a plant according to an embodiment of the present invention.
具体实施方式detailed description
为了使本发明要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合实施例与附图，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly, the present invention will be further described in detail below with reference to the embodiments and drawings. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
一方面，本发明实施例提供一种导电性和透明度高的柔性透明电极。所述柔性透明电极如图1所示，其包括柔性基底1，在所述柔性衬底1表面结合有金属导电物层2。其中，所述金属导电物层2呈植物叶脉状图案，且金属导电物为银纳米线。这样，金属导电物层2由银纳米线形成的植物叶脉状图案，由于植物在长期的自然进化过程中形成的叶脉具有其自身的特定完美脉络结构和形貌，从而使得金属导电物层2阻小，具有优异的导电性能和透光性能以及弹性。其与柔性基体1结合后，赋予柔性透明电极优异的导电性能和透光性能以及柔性性，且机械性能稳定。In one aspect, embodiments of the present invention provide a flexible transparent electrode having high conductivity and transparency. The flexible transparent electrode, as shown in FIG. 1, comprises a flexible substrate 1 on the surface of which a metal conductive layer 2 is bonded. Wherein, the metal conductive layer 2 has a plant vein pattern, and the metal conductive material is a silver nanowire. In this way, the metal conductor layer 2 is formed by the silver veins of the plant vein pattern, and the vein formed by the plant in the long-term natural evolution process has its own specific perfect vein structure and morphology, so that the metal conductor layer 2 is blocked. Small, with excellent electrical and optical properties and elasticity. When combined with the flexible substrate 1, it imparts excellent electrical conductivity, light transmission property and flexibility, and mechanical properties to the flexible transparent electrode.
在一实施例中，上述柔性透明电极所含的金属导电物层2中银纳米线植物叶脉状图案为桂花、杨树、木兰或者枫树等植物叶脉状图案。将银纳米线设置成该特定的植物叶脉状图案，通过该植物叶脉天然的完美脉络结构和形貌，也即是银纳米线在完美脉络结构中相互连接交叉形成特定的网络，有效赋予金属导电物层2优异的导电性能，以及韧性等机械性能，保证了柔性透明电极的导电性能和柔性的机械稳定性能。另外，常规的如不做植物叶脉状图案，则导电层的透明度只能由纳米线和纳米银线的空隙决定，但做了上述 植物叶脉状图案后，除了纳米线与纳米线之间的间隙，还多了特定的网络图案中叶脉之间的大间隙，有效提高了金属导电物层2的透明度。而且在本发明实施例中，金属导电物层2由纳米线植物叶脉状图案中不含有植物叶脉本体，也即是银纳米线植物叶脉状图案由纯粹的银纳米线构成。因此，其银纳米线植物叶脉状图案的金属导电物层2内阻低，导电性优异，而且透明度高，提高了其应用范围，如特别提高了其在电子皮肤中的应用效果。In one embodiment, the silver nanowire plant vein pattern in the metal conductive layer 2 contained in the flexible transparent electrode is a plant vein pattern such as sweet-scented osmanthus, poplar, magnolia or maple. The silver nanowires are arranged into the specific vein pattern of the plant, and the natural vein structure and morphology of the plant veins, that is, the silver nanowires are interconnected in a perfect vein structure to form a specific network, effectively imparting metal conduction. The excellent electrical conductivity of the layer 2 and the mechanical properties such as toughness ensure the electrical conductivity and flexible mechanical stability of the flexible transparent electrode. In addition, if the conventional leaf vein pattern is not used, the transparency of the conductive layer can only be determined by the gap between the nanowire and the nano silver wire, but the above is done. After the vein pattern of the plant, in addition to the gap between the nanowire and the nanowire, a large gap between the veins in the specific network pattern is added, which effectively improves the transparency of the metal conductive layer 2. Moreover, in the embodiment of the present invention, the metal conductive layer 2 is composed of a pure silver nanowire from the vein pattern of the nanowire plant which does not contain the plant vein body, that is, the silver nanowire plant vein pattern. Therefore, the metal conductor layer 2 of the vein pattern of the silver nanowire plant has low internal resistance, excellent electrical conductivity, and high transparency, thereby improving the application range thereof, such as particularly improving the application effect in the electronic skin.
在另一实施例中，构成植物叶脉状图案的所述银纳米线直径20-50nm，长度200μm-2cm。在具体实施例中，所述银纳米线直径50nm、长度2cm；或直径20nm、长度200um。其中，银纳米线直径50nm、长度2cm的扫描电镜图如图2a和图2b所示，该银纳米线长度长，直径为纳米级，且相邻银纳米线之间具有良好的间隙，提高了透明度。选用该长度的银纳米线，并使得其形成植物叶脉的特定完美脉络结构和形貌，有效提高了金属导电物层2的导电性能和完美脉络结构的韧性和稳定，而且提高了其透明性。In another embodiment, the silver nanowires constituting the vein pattern of the plant are 20-50 nm in diameter and 200 μm-2 cm in length. In a specific embodiment, the silver nanowires are 50 nm in diameter and 2 cm in length; or 20 nm in diameter and 200 um in length. The scanning electron micrograph of the silver nanowire with a diameter of 50 nm and a length of 2 cm is shown in FIG. 2a and FIG. 2b. The silver nanowire has a long length and a nanometer diameter, and has a good gap between adjacent silver nanowires, thereby improving the gap. transparency. The silver nanowires of this length are selected and formed into a specific perfect vein structure and morphology of the plant veins, which effectively improves the electrical conductivity of the metal conductive layer 2 and the toughness and stability of the perfect vein structure, and improves the transparency.
上述各实施例中的柔性透明电极所含的柔性基底1可以选用适用于电子皮肤的有机树脂基体，如苯二甲酸乙二醇酯(PET)、聚二甲基硅氧烷(PDMS)。该柔性基底1的其他性能，如厚度柔韧性能可以根据具体实际的应用需要如电子皮肤的性能需要进行灵活选用和控制。只要是能够有效使得上述特定图案的金属导电物层2与其结合，且符合透明要求和柔性要求的基体，均在本发明公开的范围之内。其中，聚二甲基硅氧烷(PDMS)基底可以按照如下方法制备获得：The flexible substrate 1 contained in the flexible transparent electrode in each of the above embodiments may be selected from an organic resin matrix suitable for electronic skin such as ethylene phthalate (PET) or polydimethylsiloxane (PDMS). Other properties of the flexible substrate 1, such as thickness flexibility, can be flexibly selected and controlled depending on the needs of the particular application, such as the performance of the electronic skin. Any substrate capable of effectively bonding the metal conductive layer 2 of the above specific pattern and conforming to the transparency requirements and flexibility requirements is within the scope of the present disclosure. Among them, a polydimethylsiloxane (PDMS) substrate can be obtained as follows:
优选为Dow Corning(道康宁)公司的产品SYLGARD184的PDMS，并将基本组分与固化剂按照10:1的重量比进行混合,搅拌10分钟后静置0.5-1小时去除气泡，或采用抽真空***约10分钟。在PET基底上缓缓倒下混合液进行旋涂，分两个阶段，第一阶段转速为500-1000r/min，时间10s，第二阶段转速为1000-2000r/min，时间是45s。将旋涂所得的样品置于热板上加热，温度为90-150℃，固化时间为30-60min。PDMS完全固化后将其从PET 衬底上剥离，从而得到柔软有弹性可拉伸的柔性基底。Preferably, the PDMS of the product SYLGARD 184 of Dow Corning, and the basic component and the curing agent are mixed in a weight ratio of 10:1, stirred for 10 minutes, left to stand for 0.5-1 hour to remove bubbles, or a vacuum system is used. About 10 minutes. Slowly pour the mixed solution on the PET substrate for spin coating in two stages. The first stage speed is 500-1000 r/min, the time is 10 s, the second stage speed is 1000-2000 r/min, and the time is 45 s. The sample obtained by spin coating was heated on a hot plate at a temperature of 90-150 ° C and a curing time of 30-60 min. PDMS is fully cured and then removed from PET The substrate was peeled off to obtain a flexible, elastically stretchable flexible substrate.
经测试，上述各实施例中的柔性透明电极的片电阻约为1-5Ω/sq，其透明度为82％-90％。The flexible transparent electrode in each of the above embodiments was tested to have a sheet resistance of about 1-5 Ω/sq and a transparency of 82% to 90%.
因此，本发明实施例柔性透明电极的金属导电物层2呈仿生植物叶脉状图案的银纳米线导电层，由于叶脉具有天然的完美脉络结构和形貌，使得本发明实施例柔性透明电极在具有优异的导电性能和透光性能的同时，还具有优异的柔性，机械稳定性。Therefore, the metal conductive layer 2 of the flexible transparent electrode of the embodiment of the present invention is a silver nanowire conductive layer of a bionic plant vein pattern. Since the vein has a natural perfect vein structure and morphology, the flexible transparent electrode of the embodiment of the present invention has Excellent electrical conductivity and light transmission properties, as well as excellent flexibility and mechanical stability.
另一方面，本发明实施例还提供了一种关于上文所述柔性透明电极的制备方法。该制备方法流程如图3所示，同时请参见柔性透明电极图1，包括如下步骤：In another aspect, embodiments of the present invention also provide a method of preparing the flexible transparent electrode described above. The preparation method flow is shown in FIG. 3, and the flexible transparent electrode is also shown in FIG. 1 and includes the following steps:
S01.在滤膜一面附上含有银纳米线：将银纳米线21的分散液用滤膜3过滤，使得所述银纳米线21附着在所述滤膜的一表面；S01. A silver nanowire is attached to one side of the filter membrane: the dispersion of the silver nanowire 21 is filtered by the filter membrane 3, so that the silver nanowire 21 is attached to a surface of the filter membrane;
S02.将植物叶脉、附有银纳米线的滤膜与柔性基底依次贴合：将所述滤膜3贴合在柔性基底1表面上，并使得附有所述银纳米线21的所述滤膜3表面与所述柔性基底1表面贴合，然后将制备的除去叶肉的植物叶脉4叠设在所述滤膜3的另一表面上；S02. The plant veins, the filter membrane with the silver nanowires and the flexible substrate are sequentially attached: the filter membrane 3 is attached to the surface of the flexible substrate 1 and the filter with the silver nanowires 21 attached thereto The surface of the membrane 3 is adhered to the surface of the flexible substrate 1, and then the prepared leaf veins of the removed mesophyll 4 are stacked on the other surface of the filter membrane 3;
S03.将银纳米线转印至柔性基底表面上：在所述植物叶脉4另一表面沿所述柔性基底1方向施加压力，使得所述银纳米线21转印至柔性基底1表面，在所述柔性基底1表面形成所述植物叶脉状图案导电层2。S03. Transferring the silver nanowires onto the surface of the flexible substrate: applying pressure in the direction of the flexible substrate 1 on the other surface of the plant vein 4, so that the silver nanowires 21 are transferred to the surface of the flexible substrate 1, The surface of the flexible substrate 1 forms the plant vein pattern conductive layer 2.
具体地，上述步骤S01中，将银纳米线21的分散液用滤膜过滤后，银纳米线21会被滤膜3截留并附着在其一表面上形成银纳米线层。其中，过滤的方式可以采用常规过滤如真空抽滤方式过滤，以提高过滤效率。Specifically, in the above step S01, after the dispersion of the silver nanowires 21 is filtered with a filter, the silver nanowires 21 are trapped by the filter membrane 3 and adhered to one surface thereof to form a silver nanowire layer. Among them, the filtration method can be filtered by conventional filtration such as vacuum filtration to improve filtration efficiency.
在一实施例中，所述银纳米线21的分散液浓度为1-5mg/ml。在具体实施例中，该银纳米线21的分散液可以是将银纳米线21分数至无水乙醇中利用超声分散获得均匀的分散液。其中，该银纳米线21如上文柔性透明电极中所述的直径20-50nm，长度200μm-2cm，在具体实施例中，该银纳米线21 直径50nm、长度2cm；或直径20nm、长度200μm等。In one embodiment, the silver nanowire 21 has a dispersion concentration of 1-5 mg/ml. In a specific embodiment, the dispersion of the silver nanowires 21 may be obtained by fractionally dispersing the silver nanowires 21 into absolute ethanol to obtain a uniform dispersion by ultrasonication. Wherein, the silver nanowire 21 has a diameter of 20-50 nm and a length of 200 μm-2 cm as described in the flexible transparent electrode above. In a specific embodiment, the silver nanowire 21 The diameter is 50 nm, the length is 2 cm; or the diameter is 20 nm, the length is 200 μm, and the like.
其中，所述尺寸的银纳米线21的制备方法如下：Wherein, the silver nanowire 21 of the size is prepared as follows:
利用凡尔尼置换法，在AgNO3溶液中放置钒箔进行置换反应生成银纳米线21，控制加热温度在20-100度之间，时间为2-5小时。Using the Vernier displacement method, a vanadium foil is placed in the AgNO 3 solution to carry out a displacement reaction to form a silver nanowire 21, and the heating temperature is controlled to be between 20 and 100 degrees for a period of 2 to 5 hours.
其中，AgNO3溶液的浓度优选为0.01-0.1mg/ml，其加入的量可以根据银线的量而定，如可以但不限于10ml的。Wherein, the concentration of the AgNO 3 solution is preferably 0.01-0.1 mg/ml, and the amount thereof may be determined according to the amount of the silver wire, such as, but not limited to, 10 ml.
该方法能够有效获得长度长、直接纳米级的银纳米线21，如获得银纳米线21直径20-50nm，长度200μm-2cm银纳米线。该长度的银纳米线21能够互相交织，有效保证形成导电层2的导电性能。The method can effectively obtain silver nanowires 21 of long length and direct nanometer order, such as obtaining silver nanowires 21 with a diameter of 20-50 nm and a length of 200 μm-2 cm of silver nanowires. The silver nanowires 21 of this length can be interwoven with each other, effectively ensuring the electrical conductivity of the conductive layer 2.
在另一实施例中，所述银纳米线21附在所述滤膜3表面上的厚度控制为100nm-500nm。在另一实施例中，所述滤膜为购买的醋酸纤维滤膜，孔径为0.02μm。In another embodiment, the thickness of the silver nanowires 21 attached to the surface of the filter membrane 3 is controlled to be from 100 nm to 500 nm. In another embodiment, the filter membrane is a commercially available acetate filter membrane having a pore size of 0.02 [mu]m.
通过对银纳米线21厚度或/和的滤膜3的厚度的控制，从而提高最终在柔性基底1表面形成的植物叶脉状图案导电层的质量。By controlling the thickness of the silver nanowires 21 or/and the thickness of the filter membrane 3, the quality of the plant vein pattern conductive layer finally formed on the surface of the flexible substrate 1 is improved.
上述步骤S02中，柔性基底1可以如上文柔性透明电极中所述的柔性基底1，为了节约篇幅，在此不再赘述。植物叶脉4、附有银纳米线21的滤膜3与柔性基底1贴合后，形成植物叶脉4、滤膜3和柔性基底1依次叠合的三层结构，其中银纳米线21形成的层结构设置在滤膜3与柔性基底1之间。In the above step S02, the flexible substrate 1 may be the flexible substrate 1 as described in the flexible transparent electrode above, and the details are not described herein for the sake of space saving. The plant vein 4 and the filter membrane 3 with the silver nanowire 21 are attached to the flexible substrate 1 to form a three-layer structure in which the plant vein 4, the filter membrane 3 and the flexible substrate 1 are sequentially laminated, wherein the layer formed by the silver nanowire 21 The structure is disposed between the filter membrane 3 and the flexible substrate 1.
其中，植物叶脉4的如图4所示。在一实施例中，植物叶脉4的原材料植物叶可以是桂花、杨树、木兰或者枫树等植物叶，则植物叶脉4为相应的桂花、杨树、木兰或者枫树等等植物叶脉。在具体实施例中，该植物叶脉4可以按照如下方法制备获得：Among them, the plant vein 4 is shown in Fig. 4. In one embodiment, the raw plant leaves of the plant vein 4 may be plant leaves such as sweet-scented osmanthus, poplar, magnolia or maple, and the plant veins 4 are corresponding plant veins such as sweet-scented osmanthus, poplar, magnolia or maple. In a specific embodiment, the plant vein 4 can be prepared as follows:
将选取树叶没入碱液中，加热至90-120℃，持续0.5-2小时后取出，除去腐蚀的叶肉，清洗，干燥。通过该方法能够有效除去植物叶肉，保留完整的植物叶脉，也即是保留了完整的植物叶脉特定完美的网络结构。The leaves are removed into the alkali solution, heated to 90-120 ° C, and taken out for 0.5-2 hours, and the corroded mesophyll is removed, washed and dried. By this method, the plant mesophyll can be effectively removed, and the intact plant veins are retained, that is, the complete perfect network structure of the intact plant veins is retained.
上述步骤S03中，在沿所述柔性基底1方向施加压力的作用下，由于植 物叶脉4模板或相应的作用与滤膜，使得银纳米线21与柔性基底1表面接触，从而，将植物叶脉4的脉络结构图案以银纳米线21为介质转印柔性基底1表面，使得银纳米线21在柔性基底1表面形成如植物叶脉4所具有的特定完美的叶脉网络结构图案，形成植物叶脉状图案导电层2。In the above step S03, under the action of applying pressure along the flexible substrate 1, due to planting The vein template 4 or the corresponding action and the filter film, so that the silver nanowire 21 is in contact with the surface of the flexible substrate 1, thereby transferring the choroidal structure pattern of the plant vein 4 with the silver nanowire 21 as a medium to transfer the surface of the flexible substrate 1 so that silver The nanowires 21 form a specific perfect vein network structure pattern such as that of the plant veins 4 on the surface of the flexible substrate 1, forming a plant vein pattern conductive layer 2.
一实施例中，所述压力大小压强大小为5-15MPa。通过控制施加压力的大小，在保证银纳米线21能够有效转印植物叶脉4的图案于柔性基底1表面的同时，保证了转印形成的植物叶脉状图案导电层2的质量。应当理解的是，在该大小的压力下，持续施加压力的时间应当是足够的，如时间为1-3min。In one embodiment, the pressure is about 5-15 MPa. By controlling the magnitude of the applied pressure, while ensuring that the silver nanowires 21 can effectively transfer the pattern of the plant veins 4 to the surface of the flexible substrate 1, the quality of the plant vein pattern conductive layer 2 formed by the transfer is ensured. It should be understood that under the pressure of this magnitude, the time for continuous application of pressure should be sufficient, such as a time of 1-3 min.
在进行完上述步骤S03之后，理所当然的还包括如图3所示的步骤S04：即是移除植物叶脉4模板和滤膜3。After the above step S03 is performed, it is a matter of course to include the step S04 shown in FIG. 3: that is, the removal of the plant vein 4 template and the filter membrane 3.
因此，上述柔性透明电极制备方法采用叶脉辅助干法转印法即是以植物叶脉3为模板，将银纳米线21在柔性基底1表面形成仿生植物叶脉状图案导电层2，由于叶脉3具有天然的完美脉络结构和形貌，使得制备的柔性透明电极具有优异的导电性能和优异的柔性。上述制备方法避免了将叶脉3包覆于导电层2中，这样降低了导电层2的内阻，保证了其透光性。另外，上述制备方法避免了有害化学试剂的使用，保证了其制备过程中的环保安全，而且制备工艺简单，速度快，只需在常温下进行即可，利用自然界里丰富的树叶叶脉模板，成本低廉，适合绿色低成本量产。Therefore, the above-mentioned flexible transparent electrode preparation method adopts the vein-assisted dry transfer method, that is, the plant vein 3 is used as a template, and the silver nanowire 21 forms a bionic plant vein pattern conductive layer 2 on the surface of the flexible substrate 1, since the vein 3 has natural The perfect choroid structure and morphology make the prepared flexible transparent electrode have excellent electrical conductivity and excellent flexibility. The above preparation method avoids coating the veins 3 in the conductive layer 2, which reduces the internal resistance of the conductive layer 2 and ensures its light transmittance. In addition, the above preparation method avoids the use of harmful chemical reagents, ensures environmental protection and safety during the preparation process, and has simple preparation process and high speed, and can be carried out only at normal temperature, and utilizes rich leaf vein template in nature, and costs Low cost, suitable for green and low-cost mass production.
再一方面，在上文柔性透明电极及其制备方法的基础上，本发明实施例还提供了一种电子皮肤。所述电子皮肤应该理解是包含电子皮肤应当含有的部件，如仿生皮肤本体和电极，其中，所述电极为上文本发明实施例中所述的柔性透明电极或由上文本发明实施例所述的制备方法制备获得的柔性透明电极。由于本发明实施例电子皮肤由于含有本发明实施例柔性透明电极这样，本发明实施例电子皮肤感应灵敏，而且由于电极的透明度高，其生物仿生效果优异。另外，上述实施例上文柔性透明电极还可以用于手机触屏，OLED的屏幕等。 In a further aspect, based on the above flexible transparent electrode and the preparation method thereof, the embodiment of the invention further provides an electronic skin. The electronic skin should be understood to include components that the electronic skin should contain, such as a bionic skin body and an electrode, wherein the electrode is a flexible transparent electrode as described in the above embodiments of the invention or as described in the above embodiments of the invention. Preparation Method The obtained flexible transparent electrode was prepared. Since the electronic skin of the embodiment of the present invention contains the flexible transparent electrode of the embodiment of the present invention, the electronic skin sensing of the embodiment of the present invention is sensitive, and the biomimetic effect is excellent due to the high transparency of the electrode. In addition, the above flexible transparent electrode can also be used for a touch screen of a mobile phone, a screen of an OLED, or the like.
现结合具体实例，对本发明实施例柔性透明电极及其制备方法进行进一步详细说明。The flexible transparent electrode and the preparation method thereof according to the embodiment of the present invention will be further described in detail with reference to specific examples.
实施例1Example 1
本发明提供一种柔性透明电极，其结构如图1所示，包括PET柔性基底1，在所述柔性衬底1表面结合有金属导电物层2。其中，所述金属导电物层2呈桂花叶植物叶脉状图案，且金属导电物为银纳米线，银纳米线直径50nm、长度2cm。The present invention provides a flexible transparent electrode having a structure as shown in FIG. 1, comprising a PET flexible substrate 1 on the surface of which a metal conductive layer 2 is bonded. Wherein, the metal conductive layer 2 is a vein pattern of a osmanthus leaf plant, and the metal conductive material is a silver nanowire, and the silver nanowire has a diameter of 50 nm and a length of 2 cm.
其制备方法如下，参照图3所述的工艺流程：The preparation method is as follows, referring to the process flow described in FIG. 3:
步骤S11：取3ml银纳米线分散液2次倒进瓶口放置有纤维滤膜的真空抽滤设备中，使得所述银纳米线附着在所述滤膜的一表面；Step S11: taking 3 ml of the silver nanowire dispersion into the vacuum suction device in which the fiber filter is placed 2 times, so that the silver nanowire adheres to a surface of the filter;
其中，银纳米线分散液配制方法：取配置好的长径比很大的银纳米线(直径50nm,长度2cm，如图2所示)1mg，溶于50ml无水乙醇中，通过超声分散1～2分钟或磁力搅拌10分钟，得到均匀的银线分散液，获得浓度为0.02mg/ml的银纳米线分散液；Among them, the preparation method of the silver nanowire dispersion liquid: 1 mg of a silver nanowire (a diameter of 50 nm, a length of 2 cm, as shown in FIG. 2) with a large aspect ratio is dissolved in 50 ml of absolute ethanol and dispersed by ultrasonic 1 ～2 minutes or magnetic stirring for 10 minutes to obtain a uniform silver wire dispersion to obtain a silver nanowire dispersion having a concentration of 0.02 mg/ml;
步骤S12：迅速拿起步骤S11沾有银纳米线的滤膜将其与柔性基底PET(聚对苯二甲酸乙二醇酯)相接触，然后将制备的除去叶肉的植物叶脉叠设在所述滤膜的另一表面上；Step S12: quickly pick up the filter of the silver nanowire in step S11 and contact it with the flexible substrate PET (polyethylene terephthalate), and then stack the prepared leaf veins of the removed mesophyll On the other surface of the filter membrane;
其中，制备的除去叶肉的植物叶脉的制备方法如下：The preparation method of the prepared leaf vein for removing the mesophyll is as follows:
选取用来作为模板的桂花叶树叶数片，将其泡进浓度为0.1-0.3g/mL的氢氧化钠(NaOH)碱液中，加热至90～120℃，持续0.5～2小时，取出泡烂的树叶用牙刷轻轻刷去叶肉部分或将其直接置于水龙头下用水冲洗去除叶肉部分，再将其泡在去离子水中清洗，之后取出自然烘干便可以得到如图4所示的完整的叶脉结构；Select a few leaves of osmanthus leaves used as a template, soak it in a sodium hydroxide (NaOH) lye solution with a concentration of 0.1-0.3g/mL, heat to 90-120 ° C for 0.5-2 hours, take out the bubble Gently use the toothbrush to gently remove the mesophyll section or place it directly under the tap to rinse off the flesh portion, then soak it in deionized water, then remove it and dry it to obtain the completeness shown in Figure 4. Vein structure
步骤S13：在所述植物叶脉另一表面沿所述柔性基底方向施加压强为10-15MPa的压力，使得所述银纳米线转印至柔性基底表面，在所述柔性基底表面形成所述植物叶脉状图案导电层； Step S13: applying a pressure of 10-15 MPa in the direction of the flexible substrate on the other surface of the plant vein, such that the silver nanowire is transferred to the surface of the flexible substrate, and the plant vein is formed on the surface of the flexible substrate. Patterned conductive layer;
步骤S14：30s后取走植物叶脉和滤膜，得到本实施例柔性透明电极。Step S14: After 30 s, the plant veins and the filter are removed to obtain a flexible transparent electrode of the present embodiment.
实施例2Example 2
本发明提供一种柔性透明电极，其结构如图1所示，包括PET柔性基底1，在所述柔性衬底1表面结合有金属导电物层2。其中，所述金属导电物层2呈杨树植物叶脉状图案，且金属导电物为银纳米线，银纳米线直径20nm、长度200μm。The present invention provides a flexible transparent electrode having a structure as shown in FIG. 1, comprising a PET flexible substrate 1 on the surface of which a metal conductive layer 2 is bonded. The metal conductive layer 2 has a vein pattern of poplar plants, and the metal conductive material is a silver nanowire, and the silver nanowire has a diameter of 20 nm and a length of 200 μm.
其制备方法如下，参照图3所述的工艺流程：The preparation method is as follows, referring to the process flow described in FIG. 3:
步骤S21：参照实施例1中步骤11，不同之处在于，银纳米线直径20nm、长度200μm；Step S21: Refer to step 11 in Embodiment 1, except that the silver nanowire has a diameter of 20 nm and a length of 200 μm;
步骤S22：参照实施例1中步骤12；Step S22: Refer to step 12 in Embodiment 1;
步骤S23：参照实施例1中步骤13；Step S23: refer to step 13 in Embodiment 1;
步骤S24：参照实施例1中步骤14。Step S24: Refer to step 14 in Embodiment 1.
实施例3Example 3
本发明提供一种柔性透明电极，其结构如图1所示，包括PDMS柔性基底1，在所述柔性衬底1表面结合有金属导电物层2。其中，所述金属导电物层2呈木兰植物叶脉状图案，且金属导电物为银纳米线，银纳米线直径50nm、长度2cm。The present invention provides a flexible transparent electrode having a structure as shown in FIG. 1, comprising a PDMS flexible substrate 1 having a metal conductive layer 2 bonded to the surface of the flexible substrate 1. Wherein, the metal conductive layer 2 is in the vein pattern of the magnolia plant, and the metal conductive material is a silver nanowire, and the silver nanowire has a diameter of 50 nm and a length of 2 cm.
其制备方法如下，参照图3所述的工艺流程：The preparation method is as follows, referring to the process flow described in FIG. 3:
步骤S31：参照实施例1中步骤11；Step S31: refer to step 11 in Embodiment 1;
步骤S32：参照实施例1中步骤12；Step S32: Refer to step 12 in Embodiment 1;
步骤S33：参照实施例1中步骤13；Step S33: Refer to step 13 in Embodiment 1;
步骤S34：参照实施例1中步骤14。Step S34: Refer to step 14 in Embodiment 1.
实施例4Example 4
本发明提供一种柔性透明电极，其结构如图1所示，包括PDMS柔性基底1，在所述柔性衬底1表面结合有金属导电物层2。其中，所述金属导电物层2呈 枫树植物叶脉状图案，且金属导电物为银纳米线，银纳米线直径50nm、长度2cm。The present invention provides a flexible transparent electrode having a structure as shown in FIG. 1, comprising a PDMS flexible substrate 1 having a metal conductive layer 2 bonded to the surface of the flexible substrate 1. Wherein the metal conductive layer 2 is The maple plant has a vein pattern, and the metal conductor is a silver nanowire. The silver nanowire has a diameter of 50 nm and a length of 2 cm.
其制备方法如下，参照图3所述的工艺流程：The preparation method is as follows, referring to the process flow described in FIG. 3:
步骤S41：参照实施例1中步骤11，Step S41: refer to step 11 in Embodiment 1,
步骤S42：参照实施例1中步骤12，不同之处在于，制备植物叶脉所用的碱液为浓度为0.1-0.3g/mL氢氧化钾；Step S42: Refer to step 12 in Example 1, except that the lye used for preparing plant veins is a concentration of 0.1-0.3 g/mL potassium hydroxide;
步骤S43：参照实施例1中步骤13；Step S43: Refer to step 13 in Embodiment 1;
步骤S44：参照实施例1中步骤14。Step S44: Refer to step 14 in Embodiment 1.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。 The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims (10)

  1. 一种柔性透明电极，包括柔性基底，在所述柔性衬底表面结合有金属导电物层，其特征在于：所述金属导电物层呈植物叶脉状图案，且金属导电物为银纳米线。A flexible transparent electrode comprising a flexible substrate having a metal conductive layer bonded to the surface of the flexible substrate, wherein the metal conductive layer is in a vein pattern of a plant, and the metal conductive material is a silver nanowire.
  2. 根据权利要求1所述的柔性透明电极，其特征在于：所述植物叶脉状图案为桂花、杨树、木兰或者枫树等植物叶脉状图案；The flexible transparent electrode according to claim 1, wherein the vein pattern of the plant is a vein pattern of a plant such as sweet-scented osmanthus, poplar, magnolia or maple;
    所述银纳米线直径20-50nm，长度200μm-2cm。The silver nanowires have a diameter of 20-50 nm and a length of 200 μm-2 cm.
  3. 根据权利要求2所述的柔性透明电极，其特征在于：所述银纳米线直径50nm、长度2cm；或直径20nm、长度200μm。The flexible transparent electrode according to claim 2, wherein the silver nanowire has a diameter of 50 nm and a length of 2 cm; or a diameter of 20 nm and a length of 200 μm.
  4. 根据权利要求1-4任一所述的柔性透明电极，其特征在于：所述柔性透明电极片电阻约为1-5Ω/sq；和/或The flexible transparent electrode according to any one of claims 1 to 4, wherein the flexible transparent electrode sheet has a resistance of about 1-5 Ω/sq; and/or
    所述柔性透明电极透明度为82％-90％；和/或The flexible transparent electrode has a transparency of 82%-90%; and/or
    所述柔性基底材料为聚对苯二甲酸乙二醇酯、聚二甲基硅氧烷或者聚甲基丙烯酸甲酯中的任一种。The flexible substrate material is any one of polyethylene terephthalate, polydimethylsiloxane, or polymethyl methacrylate.
  5. 一种柔性透明电极制备方法，包括如下步骤：A method for preparing a flexible transparent electrode includes the following steps:
    将银纳米线的分散液用滤膜过滤，使得所述银纳米线附着在所述滤膜的一表面；Dissolving the dispersion of the silver nanowires with a filter membrane, so that the silver nanowires are attached to a surface of the filter membrane;
    将所述滤膜贴合在柔性基底表面上，并使得附有所述银纳米线的所述滤膜表面与所述柔性基底表面贴合，然后将制备的除去叶肉的植物叶脉叠设在所述滤膜的另一表面上；Laminating the filter membrane on the surface of the flexible substrate, and bonding the surface of the filter membrane with the silver nanowires to the surface of the flexible substrate, and then stacking the prepared leaf veins of the removed mesophyll On the other surface of the filter membrane;
    在所述植物叶脉另一表面沿所述柔性基底方向施加压力，使得所述银纳米线在所述柔性基底表面形成所述植物叶脉状图案导电层。Pressure is applied in the direction of the flexible substrate on the other surface of the plant vein such that the silver nanowires form the plant vein pattern conductive layer on the surface of the flexible substrate.
  6. 根据权利要求5所述的制备方法，其特征在于：所述银纳米线附在所述滤膜表面上的厚度为100nm-500nm；The preparation method according to claim 5, wherein the silver nanowires are attached to the surface of the filter film to a thickness of 100 nm to 500 nm;
    所述滤膜为醋酸纤维滤膜，孔径为0.02μm；The filter membrane is a cellulose acetate filter membrane having a pore size of 0.02 μm;
    所述压力压强大小为5-15MPa。 The pressure pressure is 5-15 MPa.
  7. 根据权利要求5-6任一所述的制备方法，其特征在于：所述银纳米线的分散液浓度为0.02-0.1mg/ml；The preparation method according to any one of claims 5-6, wherein the concentration of the dispersion of the silver nanowires is 0.02-0.1 mg/ml;
    所述银纳米线直径20-50nm，长度200μm-2cm；The silver nanowire has a diameter of 20-50 nm and a length of 200 μm-2 cm;
    所述植物叶脉状图案为桂花杨树、木兰或者枫树等植物叶脉状图案。The vein pattern of the plant is a vein pattern of a plant such as osmanthus poplar, magnolia or maple.
  8. 根据权利要求7所述的制备方法，其特征在于：直径20-50nm、长度200um-2cm的所述银纳米线的制备方法如下：The preparation method according to claim 7, wherein the silver nanowire having a diameter of 20 to 50 nm and a length of 200 to 2 cm is prepared as follows:
    利用凡尔尼置换法，在AgNO3溶液中放置钒箔进行置换反应生成银纳米线，控制加热温度在20-100℃之间，时间为2-5小时。Using the Vernier replacement method, a vanadium foil was placed in the AgNO 3 solution to carry out a displacement reaction to form a silver nanowire, and the heating temperature was controlled to be between 20 and 100 ° C for a period of 2 to 5 hours.
  9. 根据权利要求7或8所述的制备方法，其特征在于：所述植物叶脉的制备方法如下：The preparation method according to claim 7 or 8, wherein the preparation method of the plant vein is as follows:
    将选取树叶没入碱液中，加热至90-120℃，持续0.5-2小时后取出，除去腐蚀的叶肉，清洗，干燥。The leaves are removed into the alkali solution, heated to 90-120 ° C, and taken out for 0.5-2 hours, and the corroded mesophyll is removed, washed and dried.
  10. 一种电子皮肤，包括权利要求1-4任一所述的柔性透明电极或由权利要求5-9任一所述的制备方法制备获得的柔性透明电极。 An electronic skin comprising the flexible transparent electrode of any of claims 1-4 or a flexible transparent electrode prepared by the preparation method of any of claims 5-9.
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