WO2019127553A1 - 自供电可触摸电致变色薄膜 - Google Patents

自供电可触摸电致变色薄膜 Download PDF

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WO2019127553A1
WO2019127553A1 PCT/CN2017/120314 CN2017120314W WO2019127553A1 WO 2019127553 A1 WO2019127553 A1 WO 2019127553A1 CN 2017120314 W CN2017120314 W CN 2017120314W WO 2019127553 A1 WO2019127553 A1 WO 2019127553A1
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layer
electrochromic
charge
self
powered
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PCT/CN2017/120314
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English (en)
French (fr)
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朱林
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深圳市柔宇科技有限公司
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Priority to CN201780096999.6A priority Critical patent/CN111356953A/zh
Priority to PCT/CN2017/120314 priority patent/WO2019127553A1/zh
Publication of WO2019127553A1 publication Critical patent/WO2019127553A1/zh

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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F1/153—Constructional details

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  • the invention belongs to the technical field of display, and relates to an electrochromic film, in particular to a self-powered touchable electrochromic film.
  • electrochromism Under the action of an applied electric field, the phenomenon that the material undergoes stable and reversible color change or the change of optical transmittance is called electrochromism.
  • the electrochromic material is mainly used in the field of display for electrochromic film to prepare.
  • Electrochromic device Electrochromic materials appear reversibly in color and transparency.
  • the technical problem to be solved by the present invention is to provide a self-powered, touchable electrochromic thin film that is electrochromic by self-power supply and touch without external power supply. This technology extends the field of application of electrochromism.
  • a self-powered, touchable electrochromic thin film comprising, in order: an electrode layer, a substrate layer, an electrochromic layer containing a first charge, and a triboelectric layer containing a second charge, the first charge being electrically opposite to the second charge
  • the electrode layer and the electrochromic layer are electrically conducted through the conductive holes provided on the base layer.
  • the first charge is an induced charge of a second charge.
  • the electrochromic layer is grounded through the electrode layer.
  • the triboelectric layer is made of a transparent flexible triboelectric material.
  • the transparent flexible triboelectric material is plasma-treated perfluoroethylene propylene, polyvinylidene fluoride or polyimide.
  • the electrochromic layer is made of nickel oxide, cobalt oxide, vanadium pentoxide, tungsten oxide, molybdenum oxide, titanium dioxide or Prussian blue.
  • the conductive hole includes a through hole penetrating through the base layer, and the through hole is filled with a conductive material containing a counter ion.
  • the triboelectric layer induces an external charge to reduce the amount of charge of the second charge, and the first charge in the electrochromic layer is reduced by the second charge. And flowing out through the electrode layer.
  • the triboelectric layer reduces the amount of charge of the second charge due to external electrostatic induction.
  • the triboelectric layer senses the touch of a human hand to reduce the amount of charge of the second charge.
  • the counter ions in the through holes enter the electrochromic layer due to the outflow of the first electric charge, and the oxidative epoxy reaction causes discoloration of the electrochromic layer.
  • the first charge is a positive charge and the second charge is a negative charge.
  • the conductive holes are arranged in a matrix, and the through holes of the conductive holes have a diameter of 0.1 mm to 1 mm.
  • the conductive material is a gel electrolyte containing a counter ion corresponding to the electrochromic layer.
  • the gel electrolyte is PAN, PEO or PMMA.
  • the electrochromic layer is patterned to form a plurality of independent modules, and the individual modules are respectively taken out by the electrode layers.
  • the self-powered touchable electrochromic film preferably further comprises a flexible bonding layer connecting the triboelectric layer and the electrochromic layer.
  • the flexible bonding layer is made of a thermoplastic adhesive.
  • the thermoplastic adhesive is selected from the group consisting of polydimethylsiloxane, ethylene-vinyl acetate copolymer, cellulose ester or polyacrylate.
  • a first protective layer is preferably disposed outside the electrode layer, and a second protective layer is disposed on the triboelectric layer.
  • the base layer is made of an insulating material.
  • the invention cooperates with the electrochromic layer by the electrically opposite triboelectric layer, and can convert the external mechanical energy into electric energy, and can realize the energy self-supply of the nano device.
  • the principle is that when a foreign object contacts the film, the electric charge is offset between the contact person and the triboelectric layer by contact electric power, and can be retained for a short period of time, and is originally concentrated in the electrochromic layer due to electrostatic induction.
  • the first charge (such as a positive charge) on the upper surface thus loses its induction, and flows out through the conductive holes on the substrate layer and the electrode layer (for example, back to the ground).
  • the charge transfer behavior of the contact electrification gradually becomes progressive.
  • the electrostatic induction of the triboelectric layer and the electrochromic layer reappears, the first charge is re-enriched on the surface of the electrochromic layer via the electrode layer and the conductive hole, and the film returns to the initial state, and the charge can be realized by the contact of the foreign object or not. Reciprocating motion between the electrochromic layer and the outside world (such as the earth).
  • the invention can convert the mechanical energy applied by the touch on the surface of the film into electric energy, and the electric energy can directly act on the electrochromic layer immediately to drive the discoloration, thereby realizing the discoloration function of the electrochromic film without the application of the external power supply, and the invention
  • the energy self-supplied of the nano device is realized, and the introduction of the self-powered system into the existing electrochromic device fundamentally solves the problem of energy supply of the electrochromic device, and realizes signal transmission by touch, and greatly expands electrochromism.
  • the field of application of the device is realized, and the introduction of the self-powered system into the existing electrochromic device fundamentally solves the problem of energy supply of the electrochromic device, and realizes signal transmission by touch, and greatly expands electrochromism.
  • FIG. 1 is a schematic structural view of an embodiment of the present invention.
  • a self-powered touchable electrochromic thin film comprises, in order: an electrode layer 700, a base layer 500, an electrochromic layer 400 containing a first charge, and a triboelectric layer 200 containing a second charge,
  • the electric charge of the electrode layer 700 and the electrochromic layer 400 is electrically conducted through the conductive holes 600 provided on the base layer 500.
  • the second charge-rich triboelectric layer 200 is used.
  • the second charge may be a positive charge or a negative charge.
  • the second charge is selected as a negative charge, and the first charge and the second charge are electrically charged.
  • the first charge is chosen to be a positive charge.
  • the second electric charge of the triboelectric layer 200 may be changed by external influences, and the change includes the following cases: one is that the triboelectric layer 200 senses the external electric charge to reduce the electric charge amount of the second electric charge; the second is the triboelectric layer 200 reduces the amount of charge of the second charge due to external electrostatic induction.
  • the decrease in the second charge causes the first charge in the electrochromic layer 400 to flow out through the electrode layer 700 due to the decrease in the amount of the second charge.
  • the counter ions in the through holes enter the electrochromic layer 400 due to the outflow of the first charges, and the oxidative epoxy reaction causes the electrochromic layer 400 to discolor.
  • the second electric charge (negative electric charge) is offset between the contact person and the triboelectric layer 200 by the contact electrification, that is, the triboelectric layer 200 senses the external electric charge and decreases the second.
  • the charge amount of the charge can be retained for a short period of time, and the first charge (positive charge) originally accumulated on the upper surface of the electrochromic layer 400 due to electrostatic induction is lost, and the first in the electrochromic layer 400
  • the charge is reduced by the second amount of charge, flows through the electrode layer 700 through the electrolyte in the conductive via 600, and finally returns to the ground.
  • the second electric charge (negative charge) shifting behavior of the contact electrification gradually disappears, and the electrostatic induction of the triboelectric layer 200 and the electrochromic layer 400 reappears, and the first electric charge (positive electric charge) passes through the electrode layer.
  • the conductive hole 600 is re-enriched on the surface of the electrochromic layer 400, the film returns to the initial state, and the electric charge can be reciprocated between the electrochromic layer 400 and the ground by the contact of the foreign object.
  • the invention can convert the mechanical energy applied by the touch on the surface of the film into electric energy, and the electric energy can directly act on the electrochromic layer 400 immediately to drive the discoloration, thereby realizing the discoloration function of the electrochromic film without the external power supply.
  • the mechanical energy is converted into electrical energy, and the energy self-supply of the nano device is realized.
  • the self-powered system is introduced into the existing electrochromic device, the energy supply problem of the electrochromic device is fundamentally solved.
  • the second charge can be selected to be a positive charge and the first charge selected to be a negative charge.
  • the specific implementation is the same as the above embodiment, and details are not described herein again.
  • the triboelectric layer 200 is made of a triboelectric material.
  • the surface of the triboelectric material is treated by ICP etching, so that the surface polymer chain is vertically oriented and polarized, so that the upper surface of the triboelectric material is fluorine.
  • the superior electronegativity and surface migration behavior are rich in negative charges, thereby forming a negatively charged triboelectric layer 200.
  • a triboelectric layer 200 having a positive charge can be formed.
  • the triboelectric layer 200 is preferably made of a transparent flexible triboelectric material.
  • the transparent and flexible material enables the invention to be used for a flexible display device, on the one hand to achieve a display function, and on the other hand to achieve the technical problem to be solved by the present invention. Realize the self-powered function. More preferably, the transparent flexible triboelectric material is perfluoroethylene propylene, polyvinylidene fluoride or polyimide after inductively coupled plasma treatment.
  • the triboelectric layer 200 has a thickness of 50 to 100 ⁇ m, preferably 50 ⁇ m.
  • the electrochromic layer 400 is made of nickel oxide, cobalt oxide, vanadium pentoxide, tungsten oxide, molybdenum oxide, titanium dioxide or Prussian blue. These materials can be used for the electrochromic layer, and can be made of one or more kinds in practical applications. In this embodiment, cobalt oxide can be selected.
  • the electrochromic layer 400 has a thickness of 50 to 150 nm, and is generally selected to have a thickness of 50 nm, 70 nm, 100 nm, 120 nm, 150 nm, etc., preferably 100 nm.
  • the electrochromic layer 400 itself is uncharged since the triboelectric layer 200 is always negatively charged or positively charged after being processed. After the electrochromic layer 400 is grounded, it is electrostatically induced with the triboelectric layer 200 to carry an electrical positive or negative charge opposite to the triboelectric layer 200. When the human hand is close, it can also generate electrostatic induction with the triboelectric layer 200. This induction becomes stronger as the distance approaches, and instead of the electrostatic induction of the electrochromic layer 400, the originally induced positive or negative charge is gradually lost.
  • the base layer 500 may be made of an insulating material.
  • the PET material is selected.
  • the base layer 500 is not limited to the PET material, and other insulating polymer materials such as PMMA may also be used.
  • the base layer 500 is used on the one hand as a base layer to which the electrode layer 700 is attached, or is used to conduct the electrification layer 400 and the electrode layer 700. Therefore, the base layer 500 is provided with a plurality of through holes penetrating the base layer through the laser.
  • the through hole penetrating through the base layer is formed by etching, and the through hole is filled with a conductive material containing a counter ion to form a conductive hole 600 for conducting the electrochromic layer 400 and the electrode layer 700.
  • the conductive material is a gel electrolyte containing counter ions corresponding to the electrochromic layer 400, and the counter ions in the base layer 500 enter the electrochromic layer 400 when the positive or negative charge is lost, and occur in the electrochromic layer 400.
  • the redox reaction changes the color or transmittance of the electrochromic layer 400.
  • the conductive material is preferably a transparent conductive material.
  • the gel electrolyte is PAN, PEO or PMMA.
  • the through holes are evenly arranged, and the arrangement is preferably a matrix type, and most preferably a square matrix type, the through hole diameter is 0.1 mm to 1 mm, preferably 0.5 mm in diameter, and the shape of the through hole is not limited, only It is sufficient to achieve conduction through the through.
  • the electrochromic layer 400 is patterned to form a plurality of independent modules, and each of the independent modules is correspondingly provided with a through hole, and the patterning process is usually laser splitting or yellow light. Processing, forming various patterns such as a rectangle, a diamond or a triangle, each pattern or several patterns forming a separate module, each of the independent modules being respectively connected to the corresponding electrode layer 700 through a conductive hole, and each of the independent The modules are respectively led out by the electrode layers, specifically by the patterned lines of the different electrode layers 700. Therefore, each module can be independently controlled to achieve diverse visual effects.
  • the self-powered touchable electrochromic film further includes a flexible bonding layer 300 that connects the triboelectric layer 200 and the electrochromic layer 400.
  • the flexible bonding layer 300 is made of a thermoplastic adhesive, and the thermoplastic adhesive may be selected from the group consisting of polydimethylsiloxane, ethylene-vinyl acetate copolymer, cellulose ester, polyacrylate, and the like.
  • the flexible adhesive layer 300 functions to bond the electrochromic layer 400 and the triboelectric layer 200 together to form a unitary body.
  • the role of the electrode layer 700 in the invention is to return positive charges charged on the upper surface of the electrochromic layer 400 due to electrostatic induction through the gel electrolyte-filled conductive holes 600 on the base layer 500, and the electrode layer 700 back to the ground. And directing positive charge back to the electrochromic layer 400 from the ground.
  • the material of the electrode layer 700 can be variously selected, and the electrode used in the flexible display device is applicable to the present invention.
  • the ITO layer is selected as the electrode layer 700. It can be understood that the electrode layer 700 can also be made of other conductive materials, such as a transparent conductive material or a metal material, that is, both are used as an electrode layer.
  • a first protective layer 100 is disposed outside the electrode layer 700, and a second protective layer 800 is disposed on the triboelectric layer 200 to protect the triboelectric layer 200 and the electrode layer 700 from scratches.
  • the first protective layer 100 and the second protective layer 800 may be selected from a flexible material to accommodate a flexible display device.
  • the first protective layer 100 and the second protective layer 800 may be made of materials such as PC, PET, PI, PS, etc., and the first protective layer 100 and the second protective layer 800 have a thickness of 20-100 micrometers, preferably 50 micrometers.
  • the manufacturing method is the following steps:
  • Fabricating an ITO layer attaching the ITO layer to the PET substrate by magnetron sputtering;
  • a first protective layer and a second protective layer are respectively disposed outside the ITO layer and the triboelectric layer.
  • Test object The present invention uses the following materials to make eight samples without the first protective layer and the second protective layer, numbered 1-8.
  • a self-powered touch electrochromic film is prepared, and the film has a film size of 4.5 cm x 4.5 cm.

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)

Abstract

一种自供电可触摸电致变色薄膜，依次包括：电极层（700）、基体层（500）、含第一电荷的电致变色层（400）及含第二电荷的摩擦电层（200），第一电荷与第二电荷的电性相反，所述电极层（700）与电致变色层（400）通过基体层（500）上设置的导电孔（600）通电导通。所述薄膜无需外接供电，通过自供电、触摸形成电致变色的自供电可触摸电致变色薄膜。

Description

自供电可触摸电致变色薄膜 技术领域
本发明属于显示技术领域，涉及一种电致变色薄膜，尤其涉及一种自供电可触摸电致变色薄膜。
背景技术
在外加电场的作用下，材料发生稳定、可逆的颜色变化的现象或光学透过率变化的现象，称为电致变色现象，电致变色材料在显示器领域主要用于电致变色薄膜，来制备电致变色器件。电致变色材料外观上表现为颜色和透明度的可逆变化。
但现有的电致变色薄膜技术始终摆脱不了的一个根本问题是：需要外部提供电压，并且许多电致变色材料需要高能耗才能实现高的变色效率，极大地限制了电致变色器件的发展。另外，电致变色器件在人机交互领域的应用，也仅靠电信号产生刺激响应，受限于其感应信号的单一的影响应用范围。
技术问题
但现有的电致变色薄膜技术始终摆脱不了的一个根本问题是：需要外部提供电压，并且许多电致变色材料需要高能耗才能实现高的变色效率，极大地限制了电致变色器件的发展。另外，电致变色器件在人机交互领域的应用，也仅靠电信号产生刺激响应，受限于其感应信号的单一的影响应用范围。
技术解决方案
本发明要解决的技术问题在于，针对现有技术的缺陷，提供一种无需外接供电，通过自供电、触摸形成电致变色的自供电可触摸电致变色薄膜。该技术扩展了电致变色的应用领域。
本发明解决其技术问题所采用的技术方案是：
一种自供电可触摸电致变色薄膜，依次包括：电极层、基体层、含第一电荷的电致变色层及含第二电荷的摩擦电层，第一电荷与第二电荷的电性相反，所述电极层与电致变色层通过基体层上设置的导电孔通电导通。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述第一电荷为第二电荷的感应电荷。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述电致变色层通过电极层接地。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述摩擦电层采用透明柔性摩擦电材料制成。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述透明柔性摩擦电材料采用等离子体处理后的全氟乙丙烯、聚偏氟乙烯或聚酰亚胺。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述电致变色层采用氧化镍、氧化钴、五氧化二钒、氧化钨、氧化钼、二氧化钛或普鲁士蓝制成。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述导电孔包括贯通基体层的通孔，所述通孔中填充含反离子的导电材料。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述摩擦电层感应外界的电荷而减少第二电荷的电荷量，电致变色层内的第一电荷由于第二电荷量减少而经由电极层流出。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述摩擦电层由于外界的静电感应而减少第二电荷的电荷量。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述摩擦电层感应人手的触摸而减少第二电荷的电荷量。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述通孔内的反离子由于第一电荷的流出而进入电致变色层，发生氧化环氧反应使电致变色层变色。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述第一电荷为正电荷，第二电荷为负电荷。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述导电孔为矩阵式排列，所述导电孔的通孔直径为0.1mm～1mm。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述导电材料是含电致变色层所对应反离子的凝胶电解质。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述凝胶电解质为PAN、PEO或PMMA。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述电致变色层进行图案化处理形成多个独立模块，所述独立模块各自由电极层分别引出。
进一步地，所述的自供电可触摸电致变色薄膜中，优选自供电可触摸电致变色薄膜还包括连接摩擦电层和电致变色层的柔性粘接层。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述柔性粘接层为热塑性胶黏剂制成。
进一步地，所述的自供电可触摸电致变色薄膜中，优选所述热塑性胶黏剂选择聚二甲基硅氧烷、乙烯-乙酸乙烯酯共聚物、纤维素酯或聚丙烯酸酯。
进一步地，所述的自供电可触摸电致变色薄膜中，优选在电极层外设有第一防护层，在摩擦电层设有第二防护层。
进一步地，所述的自供电可触摸电致变色薄膜中，优选基体层由绝缘材料制成。
本发明通过电性相反的摩擦电层与电致变色层配合，可将外界机械能转化为电能，可以实现纳米器件的能量自供。其原理是：在外来对象接触薄膜时，电荷在接触者和摩擦电层之间通过接触起电发生偏移，并能发生很短一段时间的滞留，原本因静电感应而富集在电致变色层上表面的第一电荷(如正电荷)因此失去感应，通过基体层上的导电孔、电极层流出(如回到地面)，外来对象远离薄膜表面时，上述接触起电的电荷偏移行为逐渐消失，摩擦电层与电致变色层的静电感应重新出现，第一电荷经由电极层、导电孔重新富集在电致变色层表面，薄膜恢复初始状态，电荷通过外来对象接触与否可以实现电荷在电致变色层和外界(如大地)间的往复运动。即本发明可将触摸对薄膜表面所施加的机械能转化为电能，该电能可立即直接作用于电致变色层，驱动变色，即可实现无外加电源供给下电致变色膜的变色功能，本发明实现了纳米器件的能量自供，将这种自供电系统引入现有电致变色器件中，则从根本上解决电致变色器件的能量供给问题，并且以触控实现信号传递，大大拓宽电致变色器件的应用领域。
附图说明
下面将结合附图及实施例对本发明作进一步说明，附图中：
图1是本发明实施例的结构示意图。
本发明最佳实施方式
为了对本发明的技术特征、目的和效果有更加清楚的理解，现对照附图详细说明本发明的具体实施方式。
如图1所示，一种自供电可触摸电致变色薄膜，依次包括：电极层700、基体层500、含第一电荷的电致变色层400及含第二电荷的摩擦电层200，第一电荷与第二电荷的电性相反，所述电极层700与电致变色层400通过基体层500上设置的导电孔600通电导通。
本发明中采用富含第二电荷的摩擦电层200，第二电荷可以是正电荷，也可以是负电荷，本实施例中第二电荷选择为负电荷，第一电荷与第二电荷的电性相反，第一电荷选择为正电荷。
摩擦电层200的第二电荷会受外界影响产生变化，这种变化包括以下情况：一是所述摩擦电层200感应外界的电荷而减少第二电荷的电荷量；二是所述摩擦电层200由于外界的静电感应而减少第二电荷的电荷量。第二电荷的减少使得电致变色层400内的第一电荷由于第二电荷量减少而经由电极层700流出。而所述通孔内的反离子由于第一电荷的流出而进入电致变色层400，发生氧化环氧反应使电致变色层400变色。
本实施例中，外来对象接触时，第二电荷(负电荷)在接触者和摩擦电层200之间通过接触起电发生偏移，即所述摩擦电层200感应外界的电荷而减少第二电荷的电荷量，并能发生很短一段时间的滞留，原本因静电感应而富集在电致变色层400上表面的第一电荷(正电荷)因此失去感应，电致变色层400内的第一电荷因第二电荷量减少，通过导电孔600中的电解质，经由电极层700流出，最后回到地面。外来对象远离膜表面时，上述接触起电的第二电荷(负电荷)偏移行为逐渐消失，摩擦电层200与电致变色层400的静电感应重 新出现，第一电荷(正电荷)经由电极层700、导电孔600重新富集在电致变色层400表面，薄膜恢复初始状态，电荷通过外来对象接触与否可以实现电荷在电致变色层400和大地间的往复运动。即本发明可将触摸对膜表面所施加的机械能转化为电能，该电能可立即直接作用于电致变色层400，驱动变色，即可实现无外加电源供给下电致变色膜的变色功能可将机械能转化为电能，实现纳米器件的能量自供，将这种自供电系统引入现有电致变色器件中，则从根本上解决电致变色器件的能量供给问题。
在另外的实施例中，第二电荷可以选择为正电荷，第一电荷选择为负电荷。其具体实施跟上述实施例一样，在此不再赘述。
摩擦电层200采用摩擦电材料制成，例如：本实施例中，摩擦电材料的表面通过ICP刻蚀处理，使其表层高分子链垂直取向、极化，使得摩擦电材料的上表面因氟超强的电负性和表面迁移行为而富含负电荷，从而形成带有负电荷的摩擦电层200。除了上述带有负电荷的摩擦电层200外，可以制成带有正电荷的摩擦电层200。所述摩擦电层200本发明优选采用透明柔性摩擦电材料制成，透明、柔性材料使得本发明能用于柔性显示器件，一方面实现显示功能，另一方面实现本发明要解决的技术问题，就实现自供电功能。更优选所述透明柔性摩擦电材料采用电感耦合等离子体处理后的全氟乙丙烯、聚偏氟乙烯或聚酰亚胺。摩擦电层200厚度为50-100μm，优选50μm。
所述电致变色层400采用氧化镍、氧化钴、五氧化二钒、氧化钨、氧化钼、二氧化钛或普鲁士蓝制成。这些材料都可以用于电致变色层，实际应用中可以任选一种或多种制成。本实施例中，可以选择氧化钴制成。电致变色层400的厚度为50-150nm，一般在厚度选择50nm、70nm、100nm、120nm、150nm等，优选100nm。
电致变色层400本身不带电，由于摩擦电层200经处理后始终带有负电荷或正电荷。电致变色层400接地后，与摩擦电层200静电感应，从而带上与摩擦电层200相反电性的正电荷或负电荷。人手靠近时也可以与摩擦电层200产生静电感应，这种感应随着距离接近而变强，取代电致变色层400的静电感应，因此原本产生的感应正电荷或负电荷逐渐流失。
基体层500可以选用绝缘材料制成，本实施例选用PET材料，在其他实施例中，基体层500也不限于PET材料制成，还可以采用其他绝缘高分子材料，如PMMA。基体层500一方面用于作为电极层700附着的基层，还是用于导通电致变色层400和电极层700通道，因此所述基体层500设有多个贯通基体层的通孔，通过激光刻蚀形成在基体层上下贯通的通孔，所述通孔中填充含反离子的导电材料，形成将电致变色层400与电极层700导通的导电孔600。所述导电材料是含电致变色层400所对应反离子的凝胶电解质，基体层500内的反离子在正电荷或负电荷流失时进入电致变色层400，在电致变色层400内发生氧化还原反应，使得电致变色层400的颜色或透光度发生变化。由于本发明薄膜可用于柔性显示器件中，导电材料优选透明导电材料。优选所述凝胶电解质为PAN、PEO或PMMA。为了实现均衡导通，通孔均匀排布，排列方式为优选矩阵式，最优选正方矩阵式，通孔直径为0.1mm～1mm，优选直径为0.5mm，通孔的形状不作限定，只需上下贯通实现导电即可。
为了增加本发明的应用范围，则所述电致变色层400进行图案化处理，形成多个独立模块，对应每个独立模块都对应设置有通孔，图案化处理通常为采用激光分割或黄光工艺处理，形成矩形、菱形或三角形等各种图案，每个图案或几个图案形成一个独立模块，每个所述独立模块各自通过导电孔与对应的电极层700联通，并且每个所述独立模块各自由电极层分别引出，具体是通过不 同的电极层700图案化线路分别引出。因此，各模块可以独立进行控制，实现多样化的视觉效果。
除了上述结构外，自供电可触摸电致变色薄膜还包括连接摩擦电层200和电致变色层400的柔性粘接层300。所述柔性粘接层300为热塑性胶黏剂制成，热塑性胶黏剂选择为聚二甲基硅氧烷、乙烯-乙酸乙烯酯共聚物、纤维素酯、聚丙烯酸酯等均可。柔性粘胶层300的作用是用于将电致变色层400和摩擦电层200粘接在一起形成一个整体。
电极层700在发明中的作用是用于将因静电感应而富集在电致变色层400上表面的正电荷通过基体层500上的填充有凝胶电解质的导电孔600、电极层700回到地面，以及将正电荷从地面引回电致变色层400。电极层700的材料可以选用多种，适用柔性显示器件中的电极都适用本发明，本实施例选择ITO层作为电极层700。可以理解地，电极层700也可以采用其他的导电材料制造，如透明导电材料或金属材料等，即均是作为电极层使用。
在电极层700外设有第一防护层100，在摩擦电层200设有第二防护层800，分别用以保护摩擦电层200和电极层700不被刮擦损坏。第一防护层100和第二防护层800可以选择柔性材料，以适应柔性显示器件。具体第一防护层100和第二防护层800可以选择PC、PET、PI、PS等材料制成，第一防护层100和第二防护层800的厚度为20-100微米，优选50微米。
制造方法为以下步骤：
1.制造ITO层：即将ITO层通过磁控溅射附着在PET基体上；
2.在PET基体层上通过激光刻蚀出阵列排布的通孔；
3.在每个通孔中都注入凝胶电解质，在PET基体层上形成贯通的导电孔；
4.在PET基体层上依次形成电致变色层、柔性粘接层和摩擦电层；
5.在ITO层和摩擦电层外分别设置第一防护层和第二防护层。
自供电可触摸电致变色薄膜性能测试：
测试仪器：示波器
测试对象：本发明采用以下原料制成编号为1-8的八个未设置第一防护层、第二防护层的样品。
Figure PCTCN2017120314-appb-000001
实验步骤：
1、根据本发明上述原料和制备步骤，制备自供电可触摸电致变色薄膜，制成的薄膜尺寸：长宽为4.5cm×4.5cm。
2、将电致变色薄膜与示波器连接，通过触摸测试电压变化并记录，重复试验，同时观察透明薄膜是否发生颜色的变化。
实验数据及结论：
Figure PCTCN2017120314-appb-000002
结果表明本发明自供电可触摸电致变色薄膜可产生足够的电压和电流驱动电致变色层变色，同时观察到上述八个样品都有从无色转变为蓝色的趋势。

Claims (21)

  1. 一种自供电可触摸电致变色薄膜，其特征在于，依次包括：电极层、基体层、含第一电荷的电致变色层及含第二电荷的摩擦电层，第一电荷与第二电荷的电性相反，所述电极层与电致变色层通过基体层上设置的导电孔通电导通。
  2. 根据权利要求1所述的自供电可触摸电致变色薄膜，其特征在于，所述第一电荷为第二电荷的感应电荷。
  3. 根据权利要求1所述的自供电可触摸电致变色薄膜，其特征在于，所述电致变色层通过电极层接地。
  4. 根据权利要求1所述的自供电可触摸电致变色薄膜，其特征在于，所述摩擦电层采用透明柔性摩擦电材料制成。
  5. 根据权利要求4所述的自供电可触摸电致变色薄膜，其特征在于，所述透明柔性摩擦电材料采用等离子体处理后的全氟乙丙烯、聚偏氟乙烯或聚酰亚胺。
  6. 根据权利要求1所述的自供电可触摸电致变色薄膜，其特征在于，所述电致变色层采用氧化镍、氧化钴、五氧化二钒、氧化钨、氧化钼、二氧化钛或普鲁士蓝制成。
  7. 根据权利要求1至6任一项所述的自供电可触摸电致变色薄膜，其特征在于，所述导电孔包括贯通基体层的通孔，所述通孔中填充含反离子的导电材料。
  8. 根据权利要求7所述的自供电可触摸电致变色薄膜，其特征在于，所述摩擦电层感应外界的电荷而减少第二电荷的电荷量，电致变色层内的第 一电荷由于第二电荷量减少而经由电极层流出。
  9. 根据权利要求8所述的自供电可触摸电致变色薄膜，其特征在于，所述摩擦电层由于外界的静电感应而减少第二电荷的电荷量。
  10. 根据权利要求8所述的自供电可触摸电致变色薄膜，其特征在于，所述摩擦电层感应人手的触摸而减少第二电荷的电荷量。
  11. 根据权利要求8所述的自供电可触摸电致变色薄膜，其特征在于，所述通孔内的反离子由于第一电荷的流出而进入电致变色层，发生氧化环氧反应使电致变色层变色。
  12. 根据权利要求1至6任一项所述的自供电可触摸电致变色薄膜，其特征在于，所述第一电荷为正电荷，第二电荷为负电荷。
  13. 根据权利要求1至6任一项所述的自供电可触摸电致变色薄膜，其特征在于，所述导电孔为矩阵式排列，所述导电孔的通孔直径为0.1mm～1mm。
  14. 根据权利要求7所述的自供电可触摸电致变色薄膜，其特征在于，所述导电材料是含电致变色层所对应反离子的凝胶电解质。
  15. 根据权利要求14所述的自供电可触摸电致变色薄膜，其特征在于，所述凝胶电解质为PAN、PEO或PMMA。
  16. 根据权利要求1至6任一项所述的自供电可触摸电致变色薄膜，其特征在于，所述电致变色层进行图案化处理形成多个独立模块，所述独立模块各自由电极层分别引出。
  17. 根据权利要求1至6任一项所述的自供电可触摸电致变色薄膜，其特征在于，自供电可触摸电致变色薄膜还包括连接摩擦电层和电致变色层的柔性粘接层。
  18. 根据权利要求17所述的自供电可触摸电致变色薄膜，其特征在于，所述柔性粘接层为热塑性胶黏剂制成。
  19. 根据权利要求18所述的自供电可触摸电致变色薄膜，其特征在于，所述热塑性胶黏剂选择聚二甲基硅氧烷、乙烯-乙酸乙烯酯共聚物、纤维素酯或聚丙烯酸酯。
  20. 根据权利要求1至6任一项所述的自供电可触摸电致变色薄膜，其特征在于，在所述电极层外设有第一防护层，在摩擦电层设有第二防护层。
  21. 根据权利要求1至6任一项所述的自供电可触摸电致变色薄膜，其特征在于，所述基体层由绝缘材料制成。
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