WO2023155833A1 - 柔性电子材料、透气透湿电子元件、柔性电路及方法 - Google Patents

柔性电子材料、透气透湿电子元件、柔性电路及方法 Download PDF

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WO2023155833A1
WO2023155833A1 PCT/CN2023/076475 CN2023076475W WO2023155833A1 WO 2023155833 A1 WO2023155833 A1 WO 2023155833A1 CN 2023076475 W CN2023076475 W CN 2023076475W WO 2023155833 A1 WO2023155833 A1 WO 2023155833A1
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yarn
fiber
ink
conductive
conductive ink
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PCT/CN2023/076475
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English (en)
French (fr)
Inventor
李翼
易杨佩奇
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宁波亨励数字科技有限公司
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Priority claimed from CN202210233167.7A external-priority patent/CN116647982A/zh
Application filed by 宁波亨励数字科技有限公司 filed Critical 宁波亨励数字科技有限公司
Publication of WO2023155833A1 publication Critical patent/WO2023155833A1/zh

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    • 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

Definitions

  • the present invention relates to the technical field of flexible electronic materials and flexible circuits, in particular to a flexible electronic material and a preparation method thereof, as well as air-permeable and moisture-permeable electronic components, flexible circuits and intelligent terminals made of the flexible electronic material.
  • printing techniques can deposit conductive materials directly on substrates.
  • Screen printing has been widely used to form conductive patterns on fabrics, but requires the use of high concentrations of conductive ink/paste, and one template corresponds to only one pattern, so ink preparation and design flexibility limit the development of this technology.
  • thicker conductive coatings affect the wearing comfort of wearable devices such as air permeability, moisture permeability, and softness.
  • inkjet printing can form a thin conductive layer, because the conductive ink has a very low viscosity, capillary penetration causes the droplets to penetrate the fabric and spread around. Therefore, the pattern resolution of inkjet printing is very poor, which cannot meet the requirements of practical applications.
  • a common solution is to coat the substrate to overcome the rough surface, but it will also reduce the wearing comfort such as air permeability, moisture permeability, and softness, which brings difficulties and challenges to the application and development of printing technology on textiles.
  • Spontaneous realization of conductive patterns by permeating conductive ink in capillary channels is a new method that can replace traditional printing techniques.
  • Hamedi (Hamedi, M.M., Ainla, A., Güder, F., Christodouleas, D.C., Fernández ⁇ Abedul, M.T. and Whitesides, G.M., 2016. Integrating electronics and microfluidics on paper. Advanced Materials, 28(25), pp.5054 -5063)
  • Hydrophobic areas are formed on hydrophilic paper by wax printing technology, so carbon nanotubes and PEDOT:PSS ink can diffuse on paper to form conductive areas.
  • Hyun Hyun, W.J., Secor, E.B., Kim, C.H., Hersam, M.C., Francis, L.F.and Frisbie, C.D., 2017.SCalable, Self ⁇ aligned Printing of Flexible Grady Micr o ⁇ superCapacitors.advanced Energy Materials, 7 (7 (7 ( 17), p.1700285) use a stamp to carve capillary channels on a film covered with a UV curable polymer, and simultaneously cure the pattern with UV light. Graphene ink can permeate in the capillary channel to realize the application of supercapacitor. However, when these technologies are applied to textiles, the polymer will fill the pores between the fibers, significantly reducing the fabric's air permeability, moisture permeability, softness and other wearing comfort.
  • the present invention provides a flexible electronic material and a preparation method thereof, a breathable and moisture-permeable electronic component made of a flexible electronic material, a flexible circuit and an intelligent terminal. and Ink-repellent materials are combined to form an ink-absorbing area by selecting ink-friendly materials, fibers or yarns, and conductive lines are prepared by diffusing conductive ink by capillary force to achieve a low-loss, low-energy production process and further solve existing problems.
  • the technology fails to balance the problem of controlling the diffusion of conductive ink and maintaining the wearing comfort of flexible electronic materials.
  • the conductive ink with low viscosity and high surface tension is dropped onto the ink-absorbing area by means of pipetting gun, dropper, inkjet printing, screen printing, and dipping.
  • the conductive ink will flow along the ink-absorbing material, fiber Or the yarn spreads until the front end of the solvent touches the ink-repellent area, which will inhibit the further diffusion of the conductive ink to improve the pattern resolution.
  • a flexible electronic material consisting of a conductive region made of an ink-absorbing material, fiber or yarn, and an insulating region made of an ink-repellent material, fiber or yarn;
  • the ink-absorbing Materials, fibers or yarns refer to materials, fibers or yarns that can absorb conductive ink, and can diffuse conductive ink through capillary force;
  • the ink-repellent materials, fibers or yarns refer to materials, fibers or yarns that do not absorb conductive ink thread, which can inhibit the spreading of conductive ink, which is oil-based or water-based.
  • the viscosity of the conductive ink is less than 20cps, the surface tension is greater than 20mN/m, and there are particles or flakes smaller than microns.
  • the viscosity range of the conductive ink is within 1-10cps, and the surface tension range is within 30-50mN/m, with nanoscale particles or flakes;
  • the conductive ink The viscosity range of the ink is within 1-20cps, the surface tension range is within 40-72mN/m, and it has nano-scale particles or flakes.
  • the ink-absorbing material, fiber or yarn has a contact angle of less than N 1 °, a yarn with a capillary tilt angle greater than N 2 ° and an effective capillary radius greater than N 3 ; the ink-repelling material, fiber or yarn Yarns with a contact angle greater than N 4 °, a capillary tilt angle less than N 5 °, a curvature greater than N 6 and an effective capillary radius less than N 7 .
  • the ink-absorbing material, fiber or yarn is cellulose material, cotton fiber or cotton yarn, keratin material, wool fiber or wool yarn, cellulose material, hemp fiber or hemp yarn thread, polyethylene terephthalate material, polyester fiber or polyester yarn, or polypropylene material, polypropylene fiber or yarn, and the ink repellent material, fiber or yarn is trifluorosilane-coated material, fiber or yarn, polydimethylsiloxane coated material, fiber or yarn, polyurethane coated material, fiber or yarn, polytetrafluoroethylene coated material, fiber or yarn, or melt spun polyvinylidene fluoride Vinyl material, fiber or yarn; for water-based conductive inks, the ink-absorbing material, fiber or yarn is cellulosic material, cotton fiber or yarn, the ink-repelling material, fiber or yarn is keratin material, Fiber or yarn, polyethylene terephthalate material, polyester fiber or yarn, polypropylene material, polypropylene fiber or yarn, and the ink repellent material,
  • the oil-based conductive ink refers to nano-silver ink, copper particles, graphene or carbon nanotube ink;
  • the water-based conductive ink refers to graphene oxide, MXene or PEDOT:PSS ink.
  • the structure of the flexible electronic material is knitted, woven, mixed 3D knitted, mixed 3D woven, non-woven, embroidered, or 3D printed.
  • the structure of the flexible electronic material is a 2-dimensional or 3-dimensional porous electronic material composed of conductive materials and insulating materials.
  • a method for preparing a flexible electronic material the flexible electronic material is composed of a conductive region and an insulating region, the conductive region is made of ink-absorbing material, fiber or yarn, and the insulating region is made of Made of ink-repelling materials, fibers or yarns;
  • the ink-absorbing materials, fibers or yarns refer to materials, fibers or yarns that can absorb conductive ink, and can diffuse conductive ink through capillary force;
  • the ink-repelling materials, fibers Or yarn refers to the material, fiber or yarn that does not absorb conductive ink, which can inhibit the diffusion of conductive ink;
  • the preparation method of the flexible electronic material includes: using a pipette gun, dropper, inkjet printing, screen printing or The dipping method drops the conductive ink onto the ink-absorbing material, fiber or yarn, the ink-absorbing material, fiber or yarn spreads the conductive ink to the whole conductive area, the conductive nanoparticles in the conductive ink move
  • Another aspect of the present invention is a breathable and moisture-permeable electronic component made of flexible electronic material
  • the flexible electronic material is composed of a conductive area and an insulating area
  • the conductive area is made of ink-absorbing material, fiber or yarn
  • the insulating area is made of ink-repelling material, fiber or yarn
  • the ink-absorbing material, fiber or yarn refers to a material, fiber or yarn that can absorb conductive ink, and can pass through the capillary of the material, fiber or yarn
  • the conductive ink is diffused by force
  • the ink repellent material refers to the material, fiber or yarn that does not absorb the conductive ink, and can inhibit the diffusion of the conductive ink.
  • the breathable and moisture-permeable electronic components are made of the flexible electronic material, and the breathable
  • the air permeability of moisture permeable electronic components is at least 7l m -2 s, and the moisture permeability is at least 31g m -2 day.
  • a method of fabricating a breathable and moisture-permeable electronic component from a flexible electronic material the flexible electronic material is composed of a conductive area and an insulating area, and the conductive area is made of an ink-absorbing material, fiber or yarn , the insulating area is made of ink-repelling material, fiber or yarn;
  • the ink-absorbing material refers to a material, fiber or yarn that can absorb conductive ink, and can diffuse conductive ink through the capillary force of the material, fiber or yarn
  • the ink-repelling material, fiber or yarn refers to the material, fiber or yarn that does not absorb conductive ink, and can inhibit the diffusion of conductive ink, and the air-permeable and moisture-permeable electronic components are made of the flexible electronic material, and the
  • the breathable and moisture-permeable electronic components have an air permeability of at least 7l m -2 s, and a moisture permeability of at least 31g m -2 day.
  • the method for making breathable and moisture-permeable electronic components from flexible electronic materials includes: using a pipette, a dropper, Inkjet printing, screen printing or dipping method drops the conductive ink onto the ink-absorbing material, fiber or yarn, the ink-absorbing material, fiber or yarn spreads the conductive ink to the whole conductive area, the conductive The conductive nanoparticles in the ink move and deposit on the material inner surface, fiber surface or yarn surface of the conductive regions.
  • the flexible circuit is made of flexible electronic material
  • the flexible electronic material is composed of conductive area and insulating area
  • the conductive area is made of ink-absorbing material, fiber or yarn
  • the insulating area is made of ink-repelling material, fiber or yarn
  • the ink-absorbing material, fiber or yarn refers to the material, fiber or yarn that can absorb conductive ink, and can diffuse conductive ink through capillary force
  • the ink-repelling material, fiber or yarn refers to a material, fiber or yarn that does not absorb conductive ink, and can inhibit the diffusion of conductive ink.
  • the flexible circuit includes resistors, capacitors, sensors or power supplies.
  • Another aspect of the present invention is an intelligent terminal made of a flexible circuit, the flexible circuit is made of a flexible electronic material or a breathable and moisture-permeable electronic component; when the flexible circuit is made of a breathable and moisture-permeable electronic component , the breathable Moisture-permeable electronic components are made of flexible electronic materials with an air permeability of at least 7l m -2 s and a moisture permeability of at least 31g m -2 day; said flexible electronic materials are composed of conductive regions and insulating regions
  • the conductive area is made of ink-absorbing materials, fibers or yarns, and the insulating area is made of ink-repelling materials, fibers or yarns;
  • the ink-absorbing yarns refer to materials, fibers that can absorb conductive ink or yarn, which can diffuse conductive ink through capillary force;
  • the ink-repellent material, fiber or yarn refers to a material, fiber or yarn that does not absorb conductive ink, and can inhibit the diffusion of conductive
  • the smart terminal refers to wearable devices, smart clothing, smart furniture, and smart devices applied in/on buildings, automobiles, trains, airplanes, ships, spacecraft, workshops or machines.
  • the present invention provides a technique for spontaneously fabricating flexible electronic materials by designing inks and textiles combined with capillary osmosis, which solves the problem of having to frequently replace templates, screens or ink cartridges in traditional printing techniques.
  • the present invention can also be combined with various textile technologies or 3D printing technologies, so the technology is very mature and the cost is low. At the same time, the process maintains the inherent properties of the textile structure, such as stretchable, bendable, breathable, and moisture-permeable properties.
  • Fig. 1 is a flow chart of an embodiment of the present invention for preparing conductive patterns on textiles through capillary osmosis.
  • Figure 2 is a schematic diagram of the dynamic contact between the ink-absorbing yarn and the ink-repelling yarn and the conductive ink.
  • Figure 3 is the contact angle of oil-based silver ink on cotton, wool, polyester, polypropylene, and nylon.
  • Fig. 4 is a schematic diagram of an embodiment of the present invention combining various textile techniques (weaving, knitting and embroidery) to realize different conductive patterns.
  • Fig. 5 is a scanning electron microscope image of conductive silver particles deposited and attached around cotton fibers in an embodiment of the present invention.
  • Fig. 6 is the resistance and resistance histogram of graphene and silver electrode prepared by the present invention.
  • Figure 7 shows the flexibility of the electrode prepared in the embodiment of the present invention in the axial and diagonal directions, as well as the air permeability and moisture permeability compared with the traditional cloth treated with polyvinylpyrrolidone, wax, and cellulose.
  • Fig. 8 is a water washing time-resistance diagram of the silver electrode prepared in the present invention.
  • Fig. 9 shows that the conductive circuit prepared by the present invention realizes the lighting of the LED lamp.
  • Fig. 10 is a capacitor prepared by capillary penetration of conductive silver ink in embroidered cotton yarn according to an embodiment of the present invention and its frequency characteristics.
  • Fig. 11 shows the heatable garment and its performance prepared by capillary penetration of conductive ink in embroidered cotton yarn according to the embodiment of the present invention.
  • Fig. 12 is a schematic diagram and performance of a wearable electronic device realized by covering different materials on graphene or silver electrodes according to an embodiment of the present invention.
  • FIG. 1 is a flow chart of the first embodiment of the present invention for preparing conductive patterns on textiles through capillary osmosis.
  • the ink-absorbing yarn and the ink-repelling yarn form a flexible electronic material.
  • the conductive area of the target is made of ink-absorbent yarn, while the ink-repellent yarn covers the rest of the area.
  • the ink-absorbing yarn is a yarn that can absorb conductive ink
  • the ink-repellent yarn is a yarn that does not absorb conductive ink.
  • the ink-absorbing and ink-repelling yarns were judged by the dynamic contact angle of the conductive ink and the yarn (Fig. 2).
  • Figure 3 shows the contact angle of oil-based nano-silver ink on cotton, wool, polyester, polypropylene, and nylon, so it can be judged that cotton, wool, and nylon are good ink-absorbing yarns.
  • conductive inks include but are not limited to oil-based nano-silver inks, copper particles, graphene and carbon nanotube inks, and water-based graphene oxide inks, MXene, PEDOT:PSS inks, with appropriate properties, including: viscosity (less than 20cps), surface tension (greater than 20mN/m), less than micron-sized particles/flakes; it is found through experiments that conductive inks preferably have nano-sized particles or flakes, and, as preferred, for oil-based conductive inks, its viscosity The range is within 1-10cps, and the surface tension range is within 30-50mN/m; for water-based conductive ink, the viscosity range of the conductive ink is within 1-20cps, and the surface tension range is within 40-72mN/m.
  • the ink-absorbing yarn is a yarn with a low oil contact angle ( ⁇ 30°), a high capillary tilt angle (>60°) and a large effective capillary radius (>1.5 ⁇ m) Thread, including: cotton, wool, hemp, polyester, polypropylene and other yarns.
  • the ink-repellent yarn has higher oil contact angle (>90°), lower capillary tilt angle ( ⁇ 10°), larger bending degree (>2) and smaller effective capillary radius ( ⁇ 1 ⁇ m), Including: trifluorosilane coated yarn, polydimethylsiloxane coated yarn, polyurethane coated yarn, polytetrafluoroethylene coated yarn, polyvinylidene fluoride yarn, etc.
  • ink-absorbing yarns are yarns with lower water contact angle ( ⁇ 30°), higher capillary tilt angle (>60°), and larger effective capillary radius (>1.5 ⁇ m) Thread, including: cotton, silk yarn.
  • Ink-repellent yarns have higher water contact angle (>90°), lower capillary tilt angle ( ⁇ 10°), larger bending degree (>2) and smaller effective capillary radius ( ⁇ 1 ⁇ m), including : Wool, polyester, polypropylene, nylon yarn, etc.
  • the structure of flexible electronic materials can be knitted, woven, mixed 3D knitted, mixed 3D woven, non-woven, embroidered, or 3D printed; or composed of conductive materials and insulating materials 2D or 3D porous electronic materials.
  • the conductive region of the target has good conductivity and can realize a variety of flexible circuit applications, such as resistors, capacitors, sensors or power supplies.
  • the present invention can also make various flexible circuits from flexible electronic materials, and then apply flexible circuits to various smart terminals, such as wearable devices, smart clothing, smart furniture, and applications in buildings, automobiles, trains, airplanes, Smart devices in/on ships, spacecraft, workshops or machines.
  • FIG. 4 is a schematic diagram of an embodiment of the present invention in combination with various textile technologies (weaving, knitting and embroidery) to realize different conductive patterns:
  • the conductive pattern was realized by weaving ink-repellent yarn (polydimethylsiloxane-coated yarn) and ink-absorbent yarn (cotton yarn) (Fig. 4d).
  • the conductive ink is dropped in the middle of the cotton yarn, and it can be observed that the ink diffuses to the left and right due to capillary force, and the color of the cotton yarn changes from white to black, while the color of the polydimethylsiloxane-coated yarn does not change. This means that the silver ink will only spread along the cotton yarn.
  • the conductive pattern was achieved by alternately knitting ink-repellent yarns (thermoplastic polyurethane coated yarns) and ink-absorbent yarns (wool yarns) (Fig. 4e).
  • ink-repellent yarns thermoplastic polyurethane coated yarns
  • wool yarns wool yarns
  • two rows of TPU-coated yarn are knitted, followed by two rows of wool yarn, followed by two rows of TPU-coated yarn. Dropping the conductive ink on the wool yarn area can form the expected conductive area through the capillary penetration and the inhibition of the conductive ink by the thermoplastic polyurethane coated yarn.
  • the conductive pattern was achieved by embroidering ink-absorbing yarn (cotton yarn) on a fluoride-coated ink-repellent material (Fig. 4f). Drop conductive ink in the square area, the ink will permeate capillary along the direction of the extension line to form a conductive area, and the length of the core line can reach 7 cm.
  • FIG. 5 is a scanning electron microscope image of conductive silver particles deposited and attached around fibers in an example of the present invention. It can be found that silver particles form a dense conductive layer between fibers.
  • Figure 6a shows the resistance of the graphene and silver electrodes prepared by the present invention, it can be found that the more conductive ink is used, the lower the resistance.
  • the highest conductivities of graphene and silver electrodes are 4.8 and 3.3 ⁇ 10 4 S/m, respectively.
  • Figure 6b shows the resistance histogram of a batch (72 electrodes) deposited from 20 ⁇ l of silver ink. The conductivity accumulated in the range of 1-5 ⁇ 10 4 S/m, indicating the high repeatability of the fabrication process.
  • FIG. 7d shows the gas permeability and moisture permeability of the electrode prepared in the present invention, compared with the traditional cloth treated with polyvinylpyrrolidone, wax and cellulose.
  • the results show that although the electrode prepared by the invention can slightly reduce the gas permeability and moisture permeability, the gas permeability is much higher than the surface treatment process of the traditional cloth treatment.
  • the air permeability of general commercial medical patches is about 7l m -2 s (liter meter -2 seconds), and the moisture permeability is about 31g m -2 day (gramm -2 days).
  • the conductive circuit implemented for the present invention can be used as a flexible circuit board, for example, to realize lighting of an LED lamp.
  • FIG. 10 is a capacitor prepared by capillary penetration of conductive silver ink in embroidered cotton yarn according to an embodiment of the present invention.
  • the ink receiving area is designed to be 0.25mm 2 .
  • the yarn capillary channels form interdigitated capacitors with a gap of 1.5 mm and a length of 10 mm.
  • the conductive ink drops in the ink-receiving area, then spontaneously capillary permeates along the yarn channel, and finally fills the entire capillary channel. After drying, the capacitance remains around 1.1pF.
  • FIG. 11 is a heatable garment prepared by capillary penetration of conductive silver ink in embroidered cotton yarn according to an embodiment of the present invention.
  • the ink receiving area is designed to be 0.25mm 2 , the gap of the serpentine channel is 1.5mm, and the length is 10mm.
  • the conductive ink drops in the ink-receiving area, then spontaneously capillary permeates along the yarn channel, and finally fills the entire capillary channel. After drying, the voltage is provided externally, and the temperature will increase with the increase of the voltage.
  • the embodiment of the present invention implements wearable electronic devices by covering different materials on graphene or silver electrodes.
  • Figure 12(a), (b) realizes the bending sensor by covering the electrode with carbon nanotubes to detect continuous wrist bending
  • Figure 12(c) realizes the temperature sensor by covering the electrode with MXene nanosheets , to detect body temperature.
  • Figure 12(e)-(h) shows the humidity sensor and the sweat detector by covering the graphene oxide on the electrode to detect the breathing rate and the amount of sweat during exercise.

Abstract

本发明公开了一种柔性电子材料、透气透湿电子元件、柔性电路及方法，涉及柔性电子材料和柔性电路技术领域。柔性电子材料由导电区域和绝缘区域组成，导电区域由吸墨材料、纤维或纱线制成，绝缘区域由拒墨材料、纤维或纱线制成；吸墨材料、纤维或纱线是指可吸附导电墨水的材料、纤维或纱线，能通过毛细管力扩散导电墨水；拒墨材料、纤维或纱线是指不吸附导电墨水的材料、纤维或纱线，能抑制导电墨水的扩散，导电墨水是油基的或水基的。本发明解决了传统的印刷技术中必须频繁更换模板、丝网或墨盒的问题，可以和各种纺织技术或3D打印技术结合，技术成熟且成本低廉，同时还保持了纺织品结构的固有特性，例如可拉伸、可弯曲、透气、透湿的特性。

Description

柔性电子材料、透气透湿电子元件、柔性电路及方法 技术领域
本发明涉及柔性电子材料和柔性电路技术领域，尤其涉及一种柔性电子材料及其制备方法，以及由该柔性电子材料制作的透气透湿电子元件、柔性电路和智能终端。
背景技术
近年来，柔性电子及智能可穿戴装置与服装等智能终端的制备广受关注。传统电子服装通常将显示器、传感器或转换器植入到日常衣物中或通过使用金属线而制成，缺点是服装穿起来不舒适，且商用的金属线的种类局限于不锈钢/涤纶混纺和银涂层尼龙线，以及在制造过程中导电层极易被机器外力损伤和磨损而产生裂纹。
打印技术可以直接在基底上沉积导电材料来替代使用金属线。丝网印刷已经被广泛用于在织物上形成导电图案，但需要使用较高浓度的导电墨水/浆料，且一个模板只对应一个图案，因此墨水制备和设计灵活性限制了该技术的发展。另外，较厚的导电涂层影响可穿戴装置透气性、透湿性、柔软性等穿戴舒适性。虽然喷墨打印可以形成较薄的导电层，但由于导电墨水的粘度非常小，毛细渗透作用会使液滴穿透织物并向四周扩散。因此，喷墨打印图案分辨率很差，无法达到实际应用的要求。常见的解决方案是在基底上涂层来克服粗糙表面，但同样会降低透气性、透湿性、柔软性等穿戴舒适性，这为打印技术在纺织品上的应用和发展带来了困难和挑战。
因此，本领域仍需要开发一种更自动化地在纺织材料上实现导电图案，同时具有清晰的图像质量和保持原本的织物结构、透气性、透湿性、柔软性等穿戴舒适性。
通过导电墨水在毛细管道里渗透自发的实现导电图案是一种可以替代传统打印技术的新方法。Hamedi(Hamedi,M.M.,Ainla,A.,Güder,F.,Christodouleas,D.C.,Fernández‐Abedul,M.T.and Whitesides,G.M.,2016.Integrating electronics and microfluidics on paper.Advanced Materials,28(25),pp.5054-5063)通过蜡印技术在亲水的纸上形成疏水区域，因此，碳纳米管和PEDOT:PSS墨水可以在纸上扩散形成导电区域。类似的，Hyun(Hyun,W.J.,Secor,E.B.,Kim,C.H.,Hersam,M.C.,Francis,L.F.and Frisbie,C.D.,2017.Scalable,self‐aligned printing of flexible graphene micro‐supercapacitors.Advanced Energy Materials,7(17),p.1700285)用***在覆盖了一层可用紫外线固化聚合物的薄膜上刻出毛细通道，同时用紫外线固化该图案。石墨烯墨水可以在毛细通道里渗透实现超级电容器的应用。但是将这些技术应用到纺织品上，聚合物会填满纤维间的孔隙，显著降低织物透气性、透湿性、柔软性等穿戴舒适性。
鉴于上述原因，本发明提供了一种柔性电子材料及其制备方法、由柔性电子材料制作的透气透湿电子元件、柔性电路和智能终端，可通过纺织技术和/或3D打印技术将吸墨材料和 拒墨材料结合在一起来，通过选择亲墨材料、纤维或纱线形成吸墨区域，通过毛细管力扩散导电墨水来制备导电线路，以实现低损耗、低耗能的生产过程，进一步解决现有技术无法平衡控制导电墨水的扩散和保持柔性电子材料穿戴舒适性的问题。
发明内容
本发明是用移液枪、滴管、喷墨打印、丝网印刷、浸渍的方法将低粘度高表面张力的导电墨水滴到吸墨区域，导电墨水因为毛细管力会沿着吸墨材料、纤维或纱线扩散，直到溶剂的前端接触拒墨区域，拒墨区域将抑制导电墨水的进一步扩散来提高图案分辨率。
一种柔性电子材料，由导电区域和绝缘区域组成，所述导电区域由吸墨材料、纤维或纱线制成，所述绝缘区域由拒墨材料、纤维或纱线制成；所述吸墨材料、纤维或纱线是指可吸附导电墨水的材料、纤维或纱线，能通过毛细管力扩散导电墨水；所述拒墨材料、纤维或纱线是指不吸附导电墨水的材料、纤维或纱线，能抑制导电墨水的扩散，所述导电墨水是油基的或水基的。
进一步的，所述导电墨水的粘度小于20cps，表面张力大于20mN/m，具有小于微米级的颗粒或薄片。作为优选，对于油基导电墨水，所述导电墨水的粘度范围在1-10cps以内，表面张力范围在30-50mN/m以内，具有纳米级的颗粒或薄片；对于水基导电墨水，所述导电墨水的粘度范围在1-20cps以内，表面张力范围在40-72mN/m以内，具有纳米级的颗粒或薄片。
进一步的，所述吸墨材料、纤维或纱线具有小于N1°的接触角，大于N2°的毛细倾斜角和大于N3的有效毛细管半径的纱线；所述拒墨材料、纤维或纱线具有大于N4°的接触角，小于N5°的毛细倾斜角，大于N6的弯曲度和小于N7的有效毛细管半径的纱线。作为优选，N1＝30，N2＝60，N3＝1.5μm，N4＝90，N5＝10，N6＝2，N7＝1μm。
进一步的，对于油基导电墨水，所述吸墨材料、纤维或纱线是纤维素材料、棉纤维或棉纱线，角蛋白材料、毛纤维或毛纱线，纤维素材料、麻纤维或麻纱线，聚对苯二甲酸乙二酯材料、涤纶纤维或涤纶纱线，或聚丙烯材料、丙纶纤维或纱线，所述拒墨材料、纤维或纱线是十三氟硅烷涂层材料、纤维或纱线，聚二甲基硅氧烷涂层材料、纤维或纱线，聚氨酯涂层材料、纤维或纱线，聚四氟乙烯涂层材料、纤维或纱线，或熔融纺聚偏二氟乙烯材料、纤维或纱线；对于水基导电墨水，所述吸墨材料、纤维或纱线是纤维素材料、棉纤维或纱线，所述拒墨材料、纤维或纱线是角蛋白材料、纤维或纱线，聚对苯二甲酸乙二酯材料、涤纶纤维或纱线，聚丙烯材料、丙纶纤维或纱线，或聚酰胺材料或尼龙纤维或纱线。
进一步的，作为优选，所述油基的导电墨水是指纳米银墨水、铜颗粒、石墨烯或碳纳米管墨水；所述水基的导电墨水是指氧化石墨烯、MXene或PEDOT:PSS墨水。
进一步的，所述柔性电子材料的结构是针织的、机织的、混合3D针织的、混合3D机织的,无纺的、刺绣的、或3D打印的。
进一步的，所述柔性电子材料的结构是由导电材料和绝缘材料组成的2维或3维的多孔电子材料。
本发明的另一方面，一种柔性电子材料的制备方法，所述柔性电子材料由导电区域和绝缘区域组成，所述导电区域由吸墨材料、纤维或纱线制成，所述绝缘区域由拒墨材料、纤维或纱线制成；所述吸墨材料、纤维或纱线是指可吸附导电墨水的材料、纤维或纱线，能通过毛细管力扩散导电墨水；所述拒墨材料、纤维或纱线是指不吸附导电墨水的材料、纤维或纱线，能抑制导电墨水的扩散；所述柔性电子材料的制备方法包括：用移液枪、滴管、喷墨打印、丝网印刷或浸渍法将所述导电墨水滴到吸墨材料、纤维或纱线，所述吸墨材料、纤维或纱线将所述导电墨水扩散至整个导电区域，所述导电墨水中的导电纳米颗粒移动并沉积在所述导电区域的材料内表面、纤维表面或纱线表面。
本发明的另一方面，一种由柔性电子材料制作的透气透湿电子元件，所述柔性电子材料由导电区域和绝缘区域组成，所述导电区域由吸墨材料、纤维或纱线制成，所述绝缘区域由拒墨材料、纤维或纱线制成；所述吸墨材料、纤维或纱线是指可吸附导电墨水的材料、纤维或纱线，能通过材料、纤维或纱线的毛细管力扩散导电墨水；所述拒墨材料是指不吸附导电墨水的材料、纤维或纱线，能抑制导电墨水的扩散，所述透气透湿电子元件由所述柔性电子材料制成，所述透气透湿电子元件的透气性至少为7l m-2s，透湿性至少为31g m-2day。
本发明的另一方面，一种由柔性电子材料制作透气透湿电子元件的方法，所述柔性电子材料由导电区域和绝缘区域组成，所述导电区域由吸墨材料、纤维或纱线制成，所述绝缘区域由拒墨材料、纤维或纱线制成；所述吸墨材料是指可吸附导电墨水的材料、纤维或纱线，能通过材料、纤维或纱线的毛细管力扩散导电墨水；所述拒墨材料、纤维或纱线是指不吸附导电墨水的材料、纤维或纱线，能抑制导电墨水的扩散，所述透气透湿电子元件由所述柔性电子材料制成，所述透气透湿电子元件的透气性至少为7l m-2s，透湿性至少为31g m-2day，所述由柔性电子材料制作透气透湿电子元件的方法包括：用移液枪、滴管、喷墨打印、丝网印刷或浸渍法将所述导电墨水滴到吸墨材料、纤维或纱线，所述吸墨材料、纤维或纱线将所述导电墨水扩散至整个导电区域，所述导电墨水中的导电纳米颗粒移动并沉积在所述导电区域的材料内表面、纤维表面或纱线表面。
本发明的另一方面，一种柔性电路，所述柔性电路由柔性电子材料制作而成，所述柔性电子材料由导电区域和绝缘区域组成，所述导电区域由吸墨材料、纤维或纱线制成，所述绝缘区域由拒墨材料、纤维或纱线制成；所述吸墨材料、纤维或纱线是指可吸附导电墨水的材料、纤维或纱线，能通过毛细管力扩散导电墨水；所述拒墨材料、纤维或纱线是指不吸附导电墨水的材料、纤维或纱线，能抑制导电墨水的扩散。
进一步的，所述柔性电路包含电阻、电容、传感器或电源。
本发明的另一方面，一种由柔性电路制作的智能终端，所述柔性电路由柔性电子材料或透气透湿电子元件制作而成；当所述述柔性电路由透气透湿电子元件制作而成时，所述透气 透湿电子元件由柔性电子材料制成，所述透气透湿电子元件的透气性至少为7l m-2s，透湿性至少为31g m-2day；所述柔性电子材料由导电区域和绝缘区域组成，所述导电区域由吸墨材料、纤维或纱线制成，所述绝缘区域由拒墨材料、纤维或纱线制成；所述吸墨纱线是指可吸附导电墨水的材料、纤维或纱线，能通过毛细管力扩散导电墨水；所述拒墨材料、纤维或纱线是指不吸附导电墨水的材料、纤维或纱线，能抑制导电墨水的扩散，所述智能终端由所述柔性电子材料制作而成。
进一步的，所述智能终端是指可穿戴装置、智能服装、智能家具，以及应用于建筑、汽车、火车、飞机、轮船、宇宙飞行器、车间或机器中/上的智能装置。
本发明提供了通过设计墨水和纺织品结合毛细渗透作用来实现自发地制造柔性电子材料的技术，解决了传统的印刷技术中必须频繁更换模板、丝网或墨盒的问题。本发明还可以和各种纺织技术或3D打印技术结合，因此技术非常成熟且成本低廉。同时，该过程保持了纺织品结构的固有特性，例如可拉伸、可弯曲、透气、透湿的特性。
附图说明
图1为本发明通过毛细渗透作用在纺织品上制备导电图案的实施例流程图。
图2为吸墨纱线和拒墨纱线与导电墨水的动态接触示意图。
图3为油基的银墨水在棉、羊毛、涤纶、丙纶、尼龙上的接触角。
图4为本发明结合多种纺织技术(机织、针织和刺绣)实现不同导电图案的实施例示意图。
图5为本发明实施例中导电银颗粒沉积附着在棉纤维周围的扫描电子显微镜图像。
图6为本发明所制备的石墨烯和银电极的电阻以及电阻直方图。
图7为本发明实施例制备电极在轴向和对角线方向的揉曲性，以及在透气率、透湿率上与传统的聚乙烯吡咯烷酮处理、蜡处理、纤维素处理后的布料对比。
图8为本发明所制备的银电极水洗时间-电阻图。
图9为本发明制备的导电线路实现LED灯点亮。
图10为本发明实施例通过导电银墨水在刺绣的棉纱线内毛细渗透作用制备的电容器及其频率特性。
图11为本发明实施例通过导电墨水在刺绣的棉纱线内毛细渗透作用制备的可加热服装及其性能。
图12为本发明实施例通过在石墨烯或银电极上覆盖不同材料来实现可穿戴电子设备示意图及性能。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚完整的描述， 显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。
图1所示为本发明通过毛细渗透作用在纺织品上制备导电图案的第一实施例流程图。
1)吸墨纱线与拒墨纱线组成一块柔性电子材料。目标的导电区域由吸墨纱线制成，而拒墨纱线覆盖其余区域。吸墨纱线为可吸附导电墨水的纱线，拒墨纱线为不吸附导电墨水的纱线。吸墨纱线和拒墨纱线通过导电墨水和纱线的动态接触角来判定(图2)。在实验过程中，将吸墨纱线改为其他吸墨材料、吸墨纤维，将拒墨纱线改为其他拒墨材料、拒墨纤维具有一样的特性。图3展示了油基的纳米银墨水在棉、羊毛、涤纶、丙纶、和尼龙上的接触角，因此可以判断棉、羊毛和尼龙是很好的吸墨纱线。
具体的，导电墨水包括但不限于油基的纳米银墨水、铜颗粒、石墨烯和碳纳米管墨水和水基的氧化石墨烯墨水、MXene、PEDOT:PSS墨水，具有适当的性能，包括：粘度(小于20cps)、表面张力(大于20mN/m)、小于微米级颗粒/薄片；通过实验发现，导电墨水最好具有纳米级的颗粒或薄片，并且，作为优选，对于油基导电墨水，其粘度范围在1-10cps以内，表面张力范围在30-50mN/m以内；对于水基导电墨水，所述导电墨水的粘度范围在1-20cps以内，表面张力范围在40-72mN/m以内。对于油基的导电墨水，吸墨纱线为具有较低的油接触角(<30°)，较高的毛细倾斜角(>60°)和较大的有效毛细管半径(>1.5μm)的纱线，包括：棉、毛、麻、涤纶、丙纶等纱线。拒墨纱线具有较高的油接触角(>90°)，较低的毛细倾斜角(<10°)，较大的弯曲度(>2)和较小的有效毛细管半径(<1μm)，包括：十三氟硅烷涂层纱线，聚二甲基硅氧烷涂层纱线、聚氨酯涂层纱线、聚四氟乙烯涂层纱线、聚偏二氟乙烯纱线等。
对于水基导电墨水，吸墨纱线为具有较低的水接触角(<30°),较高的毛细倾斜角(>60°)，和较大的有效毛细管半径(>1.5μm)的纱线，包括：棉、丝纱线。拒墨纱具有较高的水接触角(>90°)、较低的毛细倾斜角(<10°)，较大的弯曲度(>2)和较小的有效毛细管半径(<1μm)，包括：羊毛、涤纶、丙纶、尼龙纱等。
具体的，柔性电子材料的结构可以是针织的、机织的、混合3D针织的、混合3D机织的,无纺的、刺绣的、或3D打印的；或者是由导电材料和绝缘材料组成的2维或3维的多孔电子材料。
2)在毛细渗透过程中，墨水中的溶剂由于毛细管力而充满吸墨区域，墨水中的导电纳米颗粒会与溶剂一起移动并沉积在纤维表面。当液体的前端接触拒墨纱线时，扩散被抑制。
3)加热后，目标的导电区域具有很好的导电性并可以实现多种柔性电路应用，如电阻、电容、传感器或电源。
4)本发明还能由柔性电子材料制成各种柔性电路，再将柔性电路应用于各种智能终端，如可穿戴装置、智能服装、智能家具，以及应用于建筑、汽车、火车、飞机、轮船、宇宙飞行器、车间或机器中/上的智能装置。
请参阅图4，为本发明结合多种纺织技术(机织、针织和刺绣)实现不同导电图案的实施例示意图：
在一个实施例中，导电图案是由机织拒墨纱线(聚二甲基硅氧烷涂层纱线)和吸墨纱线(棉纱线)实现的(图4d)。导电墨水滴在棉纱线中间，可以观察到墨水因为毛细管力向左右两边扩散，棉纱线的颜色由白色变成黑色，而聚二甲基硅氧烷涂层纱线的颜色没有变化。这意味着银墨水只会沿着棉纱线扩散。
在一个实施例中，导电图案通过交替针织拒墨纱线(热塑性聚氨酯涂层纱线)和吸墨纱线(羊毛纱线)实现的(图4e)。在单面针织结构中，先针织两列热塑性聚氨酯涂层纱线，然后针织两列羊毛纱线，再针织两列热塑性聚氨酯涂层纱线。在羊毛纱线区域滴导电墨水，可以通过毛细渗透作用和热塑性聚氨酯涂层纱线对导电墨水的抑制作用形成预期的导电区域。
在一个实施例中，导电图案是通过在氟化物涂层的拒墨材料上刺绣吸墨纱线(棉纱线)实现的(图4f)。在正方形区域滴导电墨水，墨水会沿着延长线方向毛细渗透形成导电区域，芯线长度可以达到7厘米。
图5为本发明实施例中导电银颗粒沉积附着在纤维周围的扫描电子显微镜图像，可以发现银颗粒在纤维间形成致密的导电层。
请参阅图6a，为本发明所制备的石墨烯和银电极的电阻，可以发现使用越多导电墨水，电阻越低。石墨烯和银电极的最高电导率分别为4.8和3.3×104S/m。图6b显示了由20μl银墨水沉积的一批(72根)电极的电阻直方图。导电率在1-5×104S/m的范围内累积，表明了制造工艺的高重复性。
请参阅图7a-c，为本发明实施例制备电极在轴向和斜线方向的揉曲性。图7d为本发明制备的电极透气性、透湿性，与传统的聚乙烯吡咯烷酮处理、蜡处理、纤维素处理后的布料对比。结果显示虽然本发明制备的电极会略微降低透气性和透湿性，但透气性远高于传统处理布料的表面处理工艺。另外，一般商用医疗贴片的透气性大约7l m-2s(升米-2秒)，透湿性大约31g m-2day(克米-2天)。常用可拉伸柔性电子基底Ecoflex和PDMS的透气性约为0l m-2s，透湿性约为50g m-2day。而由本发明柔性电子材料制作的透气透湿电子元件，如电极，不仅至少达到商用医疗贴片的水平，透气性甚至可达195l m-2s，透湿性可达384g m-2day。
请参阅图8，为本发明所制备的银电极的水洗性，可发现机洗3小时后，电阻从2.1Ohms/cm上升到3.3Ohms/cm，表明了非常好的耐水洗性。
请参阅图9，为本发明实现的导电线路可以作为柔性电路板，例如实现LED灯的点亮。
请参阅图10，为本发明实施例通过导电银墨水在刺绣的棉纱线内毛细渗透作用制备的电容器。墨水接收区域设计为0.25mm2。纱线毛细通道形成叉指电容器，其间隙为1.5mm，长度是10mm。导电墨水滴在墨水接收区域里，然后自发地沿着纱线通道毛细渗透，最终填满整个毛细通道。烘干后，电容维持在1.1pF上下。
请参阅图11，为本发明实施例通过导电银墨水在刺绣的棉纱线内毛细渗透作用制备的可加热服装。墨水接收区域设计为0.25mm2，蛇形通道间隙为1.5mm，长度是10mm。导电墨水滴在墨水接收区域里，然后自发地沿着纱线通道毛细渗透，最终填满整个毛细通道。烘干后，通过外部提供电压，温度会随着电压的增大而增加。
请参阅图12，本发明实施例通过在石墨烯或银电极上覆盖不同材料来实现可穿戴电子设备。图12(a),(b)通过将碳纳米管覆盖在电极上实现弯曲传感器，检测连续的手腕的弯曲，图12(c),(d)通过将MXene纳米片覆盖在电极上来实现温度传感器，检测人体体温。图12(e)-(h)通过在电极上覆盖氧化石墨烯来展示湿度传感器和出汗检测器，检测呼吸频率和运动时的出汗的多少。

Claims (19)

  1. 一种柔性电子材料，由导电区域和绝缘区域组成，所述导电区域由吸墨材料、纤维或纱线制成，所述绝缘区域由拒墨材料、纤维或纱线制成；其特征在于，所述吸墨材料、纤维或纱线是指可吸附导电墨水的材料、纤维或纱线，能通过材料、纤维或纱线的毛细管力扩散导电墨水；所述拒墨材料、纤维或纱线是指不吸附导电墨水的材料、纤维或纱线，能抑制导电墨水的扩散，所述导电墨水是油基的或水基的。
  2. 如权利要求1所述的柔性电子材料，其特征在于，所述导电墨水的粘度小于20cps，表面张力大于20mN/m，具有小于微米级的颗粒或薄片。
  3. 如权利要求2所述的柔性电子材料，其特征在于，所述导电墨水具有纳米级的颗粒或薄片；对于油基导电墨水，所述导电墨水的粘度范围在1-10cps以内，表面张力范围在30-50mN/m以内；对于水基导电墨水，所述导电墨水的粘度范围在1-20cps以内，表面张力范围在40-72mN/m以内。
  4. 如权利要求1所述的柔性电子材料，其特征在于，所述吸墨材料、纤维或纱线具有小于N1°的接触角，大于N2°的毛细倾斜角和大于N3的有效毛细管半径的材料、纤维或纱线；所述拒墨材料或纤维或纱线具有大于N4°的接触角，小于N5°的毛细倾斜角，大于N6的弯曲度和小于N7的有效毛细管半径的材料、纤维或纱线。
  5. 如权利要求4所述的柔性电子材料，其特征在于，N1＝30，N2＝60，N3＝1.5μm，N4＝90，N5＝10，N6＝2，N7＝1μm。
  6. 如权利要求1～5中任一权利要求所述的柔性电子材料，其特征在于，对于油基导电墨水，所述吸墨材料、纤维或纱线是纤维素材料、棉纤维或棉纱线，角蛋白材料、毛纤维或毛纱线，纤维素材料、麻纤维或麻纱线，聚对苯二甲酸乙二酯材料、涤纶纤维或涤纶纱线，或聚丙烯材料、丙纶纤维或纱线，所述拒墨材料、纤维或纱线是十三氟硅烷涂层材料、纤维或纱线，聚二甲基硅氧烷涂层材料、纤维或纱线，聚氨酯涂层材料、纤维或纱线，聚四氟乙烯涂层材料、纤维或纱线，或熔融纺聚偏二氟乙烯材料、纤维或纱线；对于水基导电墨水，所述吸墨材料、纤维或纱线是纤维素材料、棉纤维或纱线，所述拒墨材料、纤维或纱线是角蛋白材料、纤维或纱线，聚对苯二甲酸乙二酯材料、涤纶纤维或纱线，聚丙烯材料、丙纶纤维或纱线，或聚酰胺材料或尼龙纤维或纱线。
  7. 如权利要求1～5所述的柔性电子材料，其特征在于，所述油基的导电墨水包括纳米银墨水，铜颗粒、石墨烯或碳纳米管墨水；所述水基的导电墨水包括氧化石墨烯、MXene或PEDOT:PSS墨水。
  8. 如权利要求1～5中任一权利要求所述的柔性电子材料，其特征在于，所述柔性电子材料的结构是针织的、机织的、混合3D针织的、混合3D机织的,无纺的、刺绣的、或3D打印的。
  9. 如权利要求1～5中任一权利要求所述的柔性电子材料，其特征在于，所述柔性电子材料的结构是由导电材料和绝缘材料组成的2维或3维的多孔电子材料。
  10. 一种柔性电子材料的制备方法，所述柔性电子材料由导电区域和绝缘区域组成，所述导电区域由吸墨材料、纤维或纱线制成，所述绝缘区域由拒墨材料、纤维或纱线制成；所述吸墨材料是指可吸附导电墨水的材料、纤维或纱线，能通过材料、纤维或纱线的毛细管力扩散导电墨水；所述拒墨材料、纤维或纱线是指不吸附导电墨水的材料、纤维或纱线，能抑制导电墨水的扩散，其特征在于，用移液枪、滴管、喷墨打印、丝网印刷或浸渍法将所述导电墨水滴到吸墨材料、纤维或纱线，所述吸墨材料、纤维或纱线将所述导电墨水扩散至整个导电区域，所述导电墨水中的导电纳米颗粒移动并沉积在所述导电区域的材料内表面、纤维表面或纱线表面。
  11. 如权利要求10所述的柔性电子材料的制备方法，其特征在于，所述柔性电子材料至少具有下列特性之一：
    所述导电墨水的粘度小于20cps，表面张力大于20mN/m，具有小于微米级的颗粒或薄片；
    所述导电墨水具有纳米级的颗粒或薄片；对于油基导电墨水，所述导电墨水的粘度范围在1-10cps以内，表面张力范围在30-50mN/m以内；对于水基导电墨水，所述导电墨水的粘度范围在1-20cps以内，表面张力范围在40-72mN/m以内；
    所述吸墨材料、纤维或纱线具有小于N1°的接触角，大于N2°的毛细倾斜角和大于N3的有效毛细管半径的材料、纤维或纱线；所述拒墨材料或纤维或纱线具有大于N4°的接触角，小于N5°的毛细倾斜角，大于N6的弯曲度和小于N7的有效毛细管半径的材料、纤维或纱线，其中，N1＝30，N2＝60，N3＝1.5μm，N4＝90，N5＝10，N6＝2，N7＝1μm；
    对于油基导电墨水，所述吸墨材料、纤维或纱线是纤维素材料、棉纤维或棉纱线，角蛋白材料、毛纤维或毛纱线，纤维素材料、麻纤维或麻纱线，聚对苯二甲酸乙二酯材料、涤纶纤维或涤纶纱线，或聚丙烯材料、丙纶纤维或纱线，所述拒墨材料、纤维或纱线是十三氟硅烷涂层材料、纤维或纱线，聚二甲基硅氧烷涂层材料、纤维或纱线，聚氨酯涂层材料、纤维或纱线，聚四氟乙烯涂层材料、纤维或纱线，或熔融纺聚偏二氟乙烯材料、纤维或纱线；对于水基导电墨水，所述吸墨材料、纤维或纱线是纤维素材料、棉纤维或纱线，所述拒墨材料、纤维或纱线是角蛋白材料、纤维或纱线，聚对苯二甲酸乙二酯材料、涤纶纤维或纱线，聚丙烯材料、丙纶纤维或纱线，或聚酰胺材料或尼龙纤维或纱线；
    所述油基的导电墨水包括纳米银墨水，铜颗粒、石墨烯或碳纳米管墨水；所述水基的导电墨水包括氧化石墨烯、MXene或PEDOT:PSS墨水；
    所述柔性电子材料的结构是针织的、机织的、混合3D针织的、混合3D机织的,无纺的、刺绣的、或3D打印的；
    所述柔性电子材料的结构是由导电材料和绝缘材料组成的2维或3维的多孔电子材料。
  12. 一种由柔性电子材料制作的透气透湿电子元件，所述柔性电子材料由导电区域和绝缘 区域组成，所述导电区域由吸墨材料、纤维或纱线制成，所述绝缘区域由拒墨材料、纤维或纱线制成；所述吸墨材料、纤维或纱线是指可吸附导电墨水的材料、纤维或纱线，能通过材料、纤维或纱线的毛细管力扩散导电墨水；所述拒墨材料是指不吸附导电墨水的材料、纤维或纱线，能抑制导电墨水的扩散，其特征在于，所述透气透湿电子元件由所述柔性电子材料制成，所述透气透湿电子元件的透气性至少为7lm-2s，透湿性至少为31gm-2day。
  13. 如权利要求12所述的由柔性电子材料制作的透气透湿电子元件，其特征在于，所述柔性电子材料至少具有下列特性之一：
    所述导电墨水的粘度小于20cps，表面张力大于20mN/m，具有小于微米级的颗粒或薄片；
    所述导电墨水具有纳米级的颗粒或薄片；对于油基导电墨水，所述导电墨水的粘度范围在1-10cps以内，表面张力范围在30-50mN/m以内；对于水基导电墨水，所述导电墨水的粘度范围在1-20cps以内，表面张力范围在40-72mN/m以内；
    所述吸墨材料、纤维或纱线具有小于N1°的接触角，大于N2°的毛细倾斜角和大于N3的有效毛细管半径的材料、纤维或纱线；所述拒墨材料或纤维或纱线具有大于N4°的接触角，小于N5°的毛细倾斜角，大于N6的弯曲度和小于N7的有效毛细管半径的材料、纤维或纱线，其中，N1＝30，N2＝60，N3＝1.5μm，N4＝90，N5＝10，N6＝2，N7＝1μm；
    对于油基导电墨水，所述吸墨材料、纤维或纱线是纤维素材料、棉纤维或棉纱线，角蛋白材料、毛纤维或毛纱线，纤维素材料、麻纤维或麻纱线，聚对苯二甲酸乙二酯材料、涤纶纤维或涤纶纱线，或聚丙烯材料、丙纶纤维或纱线，所述拒墨材料、纤维或纱线是十三氟硅烷涂层材料、纤维或纱线，聚二甲基硅氧烷涂层材料、纤维或纱线，聚氨酯涂层材料、纤维或纱线，聚四氟乙烯涂层材料、纤维或纱线，或熔融纺聚偏二氟乙烯材料、纤维或纱线；对于水基导电墨水，所述吸墨材料、纤维或纱线是纤维素材料、棉纤维或纱线，所述拒墨材料、纤维或纱线是角蛋白材料、纤维或纱线，聚对苯二甲酸乙二酯材料、涤纶纤维或纱线，聚丙烯材料、丙纶纤维或纱线，或聚酰胺材料或尼龙纤维或纱线；
    所述油基的导电墨水包括纳米银墨水，铜颗粒、石墨烯或碳纳米管墨水；所述水基的导电墨水包括氧化石墨烯、MXene或PEDOT:PSS墨水；
    所述柔性电子材料的结构是针织的、机织的、混合3D针织的、混合3D机织的,无纺的、刺绣的、或3D打印的；
    所述柔性电子材料的结构是由导电材料和绝缘材料组成的2维或3维的多孔电子材料。
  14. 一种由柔性电子材料制作透气透湿电子元件的方法，所述柔性电子材料由导电区域和绝缘区域组成，所述导电区域由吸墨材料、纤维或纱线制成，所述绝缘区域由拒墨材料、纤维或纱线制成；所述吸墨材料是指可吸附导电墨水的材料、纤维或纱线，能通过材料、纤 维或纱线的毛细管力扩散导电墨水；所述拒墨材料、纤维或纱线是指不吸附导电墨水的材料、纤维或纱线，能抑制导电墨水的扩散，所述透气透湿电子元件由所述柔性电子材料制成，所述透气透湿电子元件的透气性至少为7lm-2s，透湿性至少为31gm-2day，其特征在于，用移液枪、滴管、喷墨打印、丝网印刷或浸渍法将所述导电墨水滴到吸墨材料、纤维或纱线，所述吸墨材料、纤维或纱线将所述导电墨水扩散至整个导电区域，所述导电墨水中的导电纳米颗粒移动并沉积在所述导电区域的材料内表面、纤维表面或纱线表面。
  15. 如权利要求14所述的由柔性电子材料制作透气透湿电子元件的方法，其特征在于，所述柔性电子材料至少具有下列特性之一：
    所述导电墨水的粘度小于20cps，表面张力大于20mN/m，具有小于微米级的颗粒或薄片；
    所述导电墨水具有纳米级的颗粒或薄片；对于油基导电墨水，所述导电墨水的粘度范围在1-10cps以内，表面张力范围在30-50mN/m以内；对于水基导电墨水，所述导电墨水的粘度范围在1-20cps以内，表面张力范围在40-72mN/m以内；
    所述吸墨材料、纤维或纱线具有小于N1°的接触角，大于N2°的毛细倾斜角和大于N3的有效毛细管半径的材料、纤维或纱线；所述拒墨材料或纤维或纱线具有大于N4°的接触角，小于N5°的毛细倾斜角，大于N6的弯曲度和小于N7的有效毛细管半径的材料、纤维或纱线，其中，N1＝30，N2＝60，N3＝1.5μm，N4＝90，N5＝10，N6＝2，N7＝1μm；
    对于油基导电墨水，所述吸墨材料、纤维或纱线是纤维素材料、棉纤维或棉纱线，角蛋白材料、毛纤维或毛纱线，纤维素材料、麻纤维或麻纱线，聚对苯二甲酸乙二酯材料、涤纶纤维或涤纶纱线，或聚丙烯材料、丙纶纤维或纱线，所述拒墨材料、纤维或纱线是十三氟硅烷涂层材料、纤维或纱线，聚二甲基硅氧烷涂层材料、纤维或纱线，聚氨酯涂层材料、纤维或纱线，聚四氟乙烯涂层材料、纤维或纱线，或熔融纺聚偏二氟乙烯材料、纤维或纱线；对于水基导电墨水，所述吸墨材料、纤维或纱线是纤维素材料、棉纤维或纱线，所述拒墨材料、纤维或纱线是角蛋白材料、纤维或纱线，聚对苯二甲酸乙二酯材料、涤纶纤维或纱线，聚丙烯材料、丙纶纤维或纱线，或聚酰胺材料或尼龙纤维或纱线；
    所述油基的导电墨水包括纳米银墨水，铜颗粒、石墨烯或碳纳米管墨水；所述水基的导电墨水包括氧化石墨烯、MXene或PEDOT:PSS墨水；
    所述柔性电子材料的结构是针织的、机织的、混合3D针织的、混合3D机织的,无纺的、刺绣的、或3D打印的；
    所述柔性电子材料的结构是由导电材料和绝缘材料组成的2维或3维的多孔电子材料。
  16. 一种柔性电路，其特征在于，所述柔性电路由柔性电子材料制作而成，所述柔性电子材料由导电区域和绝缘区域组成，所述导电区域由吸墨材料、纤维或纱线制成，所述绝缘 区域由拒墨材料、纤维或纱线制成，所述吸墨材料、纤维或纱线是指可吸附导电墨水的材料、纤维或纱线，能通过材料、纤维或纱线的毛细管力扩散导电墨水，所述拒墨材料、纤维或纱线是指不吸附导电墨水的材料、纤维或纱线，能抑制导电墨水的扩散。
  17. 如权利要求16所述柔性电路，其特征在于，所述柔性电路包含电阻、电容、传感器或电源。
  18. 一种由柔性电路制作的智能终端，其特征在于，所述柔性电路由柔性电子材料或透气透湿电子元件制作而成；其中，当所述述柔性电路由透气透湿电子元件制作而成时，所述透气透湿电子元件由柔性电子材料制成，所述透气透湿电子元件的透气性至少为7lm-2s，透湿性至少为31gm-2day；所述柔性电子材料由导电区域和绝缘区域组成，所述导电区域由吸墨材料、纤维或纱线制成，所述绝缘区域由拒墨材料、纤维或纱线制成，所述吸墨材料、纤维或纱线是指可吸附导电墨水的材料、纤维或纱线，能通过材料、纤维或纱线的毛细管力扩散导电墨水，所述拒墨材料、纤维或纱线是指不吸附导电墨水的材料、纤维或纱线，能抑制导电墨水的扩散。
  19. 如权利要求18所述由柔性电路制作的智能终端，其特征在于，所述智能终端是指可穿戴装置、智能服装、智能家具，以及应用于建筑、汽车、火车、飞机、轮船、宇宙飞行器、车间或机器中/上的智能装置。
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