CN113296327A - Electrochromic display device and preparation method thereof - Google Patents
Electrochromic display device and preparation method thereof Download PDFInfo
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- CN113296327A CN113296327A CN202110601803.2A CN202110601803A CN113296327A CN 113296327 A CN113296327 A CN 113296327A CN 202110601803 A CN202110601803 A CN 202110601803A CN 113296327 A CN113296327 A CN 113296327A
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- 239000003792 electrolyte Substances 0.000 claims abstract description 49
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 239000003086 colorant Substances 0.000 claims abstract description 13
- 229920000547 conjugated polymer Polymers 0.000 claims description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 20
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 239000002033 PVDF binder Substances 0.000 claims description 18
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 18
- 229920001046 Nanocellulose Polymers 0.000 claims description 17
- 239000013078 crystal Substances 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- -1 ruthenium ions Chemical class 0.000 claims description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 14
- 239000002608 ionic liquid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229910052707 ruthenium Inorganic materials 0.000 claims description 12
- 239000011245 gel electrolyte Substances 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
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- 230000000694 effects Effects 0.000 abstract description 4
- 238000010586 diagram Methods 0.000 description 6
- QIYMZTXOQUJMML-UHFFFAOYSA-N 4-methyl-1,3-dioxolan-2-one;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CC1COC(=O)O1 QIYMZTXOQUJMML-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
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Classifications
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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
- G02F1/1514—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 characterised by the electrochromic material, e.g. by the electrodeposited material
- G02F1/1516—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 characterised by the electrochromic material, e.g. by the electrodeposited material comprising organic material
- G02F1/15165—Polymers
-
- 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
-
- 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
- G02F1/155—Electrodes
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- Physics & Mathematics (AREA)
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- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention provides an electrochromic display device and a preparation method thereof. The electrochromic display device comprises a flexible substrate, an electrode layer located on the flexible substrate, an electrochromic layer located on the electrode layer and an electrolyte layer located on the electrochromic layer, wherein the electrochromic layer comprises a plurality of first electrochromic layers and a plurality of second electrochromic layers which are distributed in an array mode, and the colors displayed after the first electrochromic layers and the second electrochromic layers are electrified are different. According to the invention, the electrochromic layer is divided into the plurality of first electrochromic layers and the plurality of second electrochromic layers which are distributed in an array manner, the colors displayed by the first electrochromic layers and the second electrochromic layers after being electrified are different, and the different electrochromic layers are electrified, so that the color development units can be independently controlled, the purpose of different color development is achieved, and the controllable multicolor electrochromic display effect is realized.
Description
Technical Field
The invention relates to the technical field of display, in particular to an electrochromic display device and a preparation method thereof.
Background
Conjugated polymers are a class of high molecular materials that have conjugated pi bonds and can be converted from insulators to semiconductors or conductors by chemical or electrochemical doping. In the electrochemical doping process, the color change is generally accompanied by redox reaction, and the conjugated polymer with reversible color and transparency change under the applied electric field is called electrochromic polymer. The conjugated polymer is mainly characterized in that different absorption peaks can be generated according to different charge transfer from coordination metal to coordination monomer, so that different colors can be displayed, and a device with a controllable color change function prepared by using the conjugated polymer material is called an electrochromic display device.
The controllable electrochromic display device in the prior art can only display one color, and the potential change of the whole display device is consistent, so that the color developing unit cannot be controlled independently. Therefore, it is necessary to improve this defect.
Disclosure of Invention
The embodiment of the invention provides an electrochromic display device, which is used for solving the technical problems that the electrochromic display device in the prior art can only display one color, the potential change of the whole display device is consistent, and a color developing unit cannot be controlled independently.
An embodiment of the present invention provides an electrochromic display device, including: flexible substrate, be located electrode layer on the flexible substrate, be located electrochromic layer on the electrode layer and being located electrolyte layer on the electrochromic layer, wherein, electrochromic layer includes a plurality of first electrochromic layers and a plurality of second electrochromic layers that the array distributes, first electrochromic layer with the colour that shows after the second electrochromic layer circular telegram is different.
In the electrochromic display device according to the embodiment of the present invention, the first electrochromic layer and the second electrochromic layer are a conjugated polymer containing a divalent ruthenium ion and a conjugated polymer containing a ferrous ion, respectively.
In the electrochromic display device provided by the embodiment of the invention, the molecular general formulas of the conjugated polymer containing the divalent ruthenium ion and the conjugated polymer containing the ferrous ion are respectively
In the electrochromic display device provided by the embodiment of the invention, the electrolyte layer comprises a conductive film positioned on the surface of the electrochromic layer far away from the electrode layer and an electrolyte membrane positioned on the surface of the conductive film far away from the electrochromic layer.
In the electrochromic display device provided by the embodiment of the invention, the material of the conductive film is a mixture of polyvinylidene fluoride and nanocellulose crystal, and the material of the electrolyte film is an ionic liquid electrolyte or a lithium gel electrolyte.
In the electrochromic display device provided by the embodiment of the invention, the conductivity of the electrolyte layer is greater than or equal to 4.0 millisiemens per centimeter and less than or equal to 4.5 millisiemens per centimeter.
In the electrochromic display device provided by the embodiment of the invention, the electrochromic display device further comprises an external power supply, wherein a first end of the external power supply is electrically connected with the electrode layer, and a second end of the external power supply is electrically connected with a pen point of the electronic pen.
The embodiment of the invention also provides a preparation method of the electrochromic display device, which comprises the following steps: s1, providing a flexible substrate; s2, preparing an electrode layer on the flexible substrate; s3, preparing an electrochromic layer on the electrode layer, wherein the electrochromic layer comprises a plurality of first electrochromic layers and a plurality of second electrochromic layers which are distributed in an array, and the colors displayed by the first electrochromic layers and the second electrochromic layers are different after being electrified; s4, preparing an electrolyte layer on the electrochromic layer.
In the electrochromic display device according to an embodiment of the present invention, the first electrochromic layer and the second electrochromic layer are a conjugated polymer containing a divalent ruthenium ion and a conjugated polymer containing a ferrous ion, respectively, and the step S3 includes: and respectively dissolving the conjugated polymer containing divalent ruthenium ions and the conjugated polymer containing ferrous ions in deionized water to prepare a first electrochromic layer aqueous solution and a second electrochromic layer aqueous solution, wherein the mass fraction ratio of the conjugated polymer containing divalent ruthenium ions and the conjugated polymer containing ferrous ions to the deionized water is in the range of 1: [80, 150 ].
In the electrochromic display device according to the embodiment of the present invention, the step S4 includes: preparing a mixed solution of polyvinylidene fluoride, dimethylformamide and nanocellulose crystal, wherein the mass fraction ratio of the polyvinylidene fluoride, the dimethylformamide and the nanocellulose crystal is 100: [400, 800]: [5, 10 ]; applying the mixed solution on the electrochromic layer to form a conductive film; an ionic liquid electrolyte or a lithium gel electrolyte is applied on the conductive film to form an electrolyte membrane.
Has the advantages that: an electrochromic display device provided in an embodiment of the present invention includes: the flexible substrate, be located the electrode layer on the flexible substrate, be located the electrochromic layer on the electrode layer and be located the electrolyte layer on the electrochromic layer, wherein, the electrochromic layer includes a plurality of first electrochromic layers and a plurality of second electrochromic layers that the array distributes, and the colour that shows is different after first electrochromic layer and second electrochromic layer circular telegram. According to the invention, the electrochromic layer is divided into the plurality of first electrochromic layers and the plurality of second electrochromic layers which are distributed in an array manner, the colors displayed by the first electrochromic layers and the second electrochromic layers after being electrified are different, and the different electrochromic layers are electrified, so that the color development units can be independently controlled, the purpose of different color development is achieved, and the controllable multicolor electrochromic display effect is realized.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below.
Fig. 1 is a schematic diagram of a basic structure of an electrochromic display device according to an embodiment of the present invention.
Fig. 2a and fig. 2b are schematic diagrams illustrating a display principle of an electrochromic display device according to an embodiment of the present invention.
Fig. 3 is a flowchart of a method for manufacturing an electrochromic display device according to an embodiment of the present invention.
Fig. 4a to 4e are schematic diagrams of basic structures of components in a process of manufacturing an electrochromic display device according to an embodiment of the present invention.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. In the drawings, the size and thickness of components illustrated in the drawings are not to scale for clarity and ease of understanding and description.
As shown in fig. 1, which is a schematic diagram of a basic structure of an electrochromic display device according to an embodiment of the present invention, the electrochromic display device includes: the flexible substrate 10, be located electrode layer 20 on the flexible substrate 10, be located electrochromic layer 30 on the electrode layer 20 and be located electrolyte layer 40 on the electrochromic layer 30, wherein, electrochromic layer 30 includes a plurality of first electrochromic layers 301 and a plurality of second electrochromic layers 302 that the array distributes, first electrochromic layer 301 with the colour that shows is different after second electrochromic layer 302 circular telegram.
The electrochromic layer 30 refers to a film layer that undergoes an electrochemical redox reaction under the action of an external electric field, and loses electrons to change the color of the material. In the embodiment of the present invention, the electrochromic layer 30 is divided into a plurality of first electrochromic layers 301 and a plurality of second electrochromic layers 302 distributed in an array, and one of the electrochromic layers is separately energized, so that the energized electrochromic layer is separately controlled to change color, and the colors displayed after the first electrochromic layer 301 and the second electrochromic layer 302 are energized are different, so that the separately controlled multicolor display can be realized.
In one embodiment, the first electrochromic layer 301 and the second electrochromic layer 302 are a conjugated polymer containing a divalent ruthenium ion and a conjugated polymer containing a ferrous ion, respectively, wherein the divalent ruthenium ion and the ferrous ion are coordination metals, and the conjugated polymer is a coordination monomer, and when power is applied, different absorption peaks are generated according to different charge transfer from the coordination metal to the coordination monomer, thereby displaying different colors. The conjugated polymer containing divalent ruthenium ions turns orange after being electrified, and the conjugated polymer containing ferrous ions turns blue after being electrified.
In one embodiment, the molecular formulas of the conjugated polymer containing divalent ruthenium ions and the conjugated polymer containing ferrous ions are respectively
In one embodiment, the electrolyte layer 40 includes a conductive film (not shown) on a surface of the electrochromic layer 30 away from the electrode layer 20 and an electrolyte film (not shown) on a surface of the conductive film away from the electrochromic layer 30. Specifically, the conductive film can increase the strength of the electrochromic display device, prevent the electrochromic display device from being scratched in the using process, increase the conductivity of the electrochromic display device, and improve the coloring efficiency of the electrochromic layer 30. In one embodiment, the conductivity of the electrolyte layer 40 comprising the conductive film is greater than or equal to 4.0 millisiemens per centimeter and less than or equal to 4.5 millisiemens per centimeter.
In one embodiment, the material of the conductive film is a mixture of polyvinylidene fluoride and nanocellulose crystal, and the material of the electrolyte membrane is an ionic liquid electrolyte or a lithium gel electrolyte.
It should be noted that the polyvinylidene fluoride material has excellent mechanical, electrical and chemical resistance, and can improve the scratch resistance of the electrochromic display device. The nano cellulose crystal material is a reproducible natural polymer material, has the superior performances of huge specific surface area, high strength, stronger adsorbability, high hydrophilicity, transparency and the like, is very suitable to be used as a polymer nano filler, and can also improve the ionic conductivity of the electrolyte membrane and improve the coloring efficiency of the electrochromic layer 30.
In particular, the first table further illustrates the effect of the polyvinylidene fluoride and nanocellulose crystals, and the electrolyte layer including the polyvinylidene fluoride and nanocellulose crystals has better scratch resistance and the conductivity of the device is increased compared to the electrolyte layer not including the polyvinylidene fluoride and nanocellulose crystals.
Watch 1
The scanning electron microscope is a microscopic morphology observation means between the transmission electron microscope and the optical microscope, and can directly utilize the material performance of the surface material of the sample to carry out microscopic imaging.
The ionic liquid is a substance composed of ions and is in a liquid state at a relatively low temperature (generally lower than 100 ℃), and the ionic liquid is an ionic compound composed of anions and cations, so that charge transfer can be realized and the ionic liquid has excellent ionic conductivity compared with a conventional organic solvent or water. As such, since the birth of the ionic liquid, it has been expected to be applied to the electrochemical field such as an electrolyte. The present invention can employ an ionic liquid electrolyte as a material of the electrolyte membrane, and commonly used ionic liquid electrolytes such as: 1-Ethyl-3-methylimidazolium bis (fluoromethylsulfonyl) imide (EMBTI).
In view of safety and stability, a lithium ion solid electrolyte material having high conductivity is required, and a solid lithium ion gel electrolyte, i.e., a lithium gel electrolyte, can be obtained by mixing a lithium ion liquid with a polymer or an inorganic nano-ion to form a lithium ion gel. The present invention may employ a lithium gel electrolyte as a material of the electrolyte membrane, and commonly used lithium gel electrolytes such as: lithium perchlorate-polymethyl methacrylate-propylene carbonate (LiClO)4-PMMA-PC), lithium perchlorate-perchloric acid-polymethyl methacrylate-propylene carbonate (LiClO)4-HClO4-PMMA-PC)。
In one embodiment, the electrochromic display device further comprises an external power source 50, wherein a first end of the external power source 50 is electrically connected with the electrode layer 20, and a second end of the external power source 50 is electrically connected with a pen tip of the electronic pen 60. It is understood that the electrochromic display device is provided with an electric field by an external power source 50, and when the tip of the electronic pen 60 is in contact with the electrolyte layer 40, it is equivalent to electrifying the electrochromic layer 30, so that the electrochromic layer 30 electrochemically reacts to display different colors. When the tip of the electronic pen 60 is disconnected from the electrolyte layer 40, the electrochromic display device is restored to the original state, i.e., does not display any color.
In one embodiment, the first terminal of the external power source 50 is a positive terminal, the second terminal of the external power source 50 is a negative terminal, and the voltage of the external power source 50 is-1.5 volts. In other embodiments, the first terminal of the external power source 50 may be a negative terminal, the second terminal of the external power source 50 may be a positive terminal, and the voltage value of the external power source 50 is 1.5 v.
In one embodiment, the external power source 50 and the electronic pen 60 are integrally formed, i.e., the external power source 50 can be embedded in the electronic pen 60.
Next, referring to fig. 2a and fig. 2b, schematic diagrams of a display principle of an electrochromic display device according to an embodiment of the present invention are shown, where the electrochromic display device includes: the flexible substrate 10, be located electrode layer 20 on the flexible substrate 10, be located electrochromic layer 30 on the electrode layer 20 and be located electrolyte layer 40 on the electrochromic layer 30, wherein, electrochromic layer 30 includes a plurality of first electrochromic layers 301 and a plurality of second electrochromic layers 302 that the array distributes, first electrochromic layer 301 with the colour that shows is different after second electrochromic layer 302 circular telegram. Wherein the electrochromic display device further comprises an external power source 50, a first end of the external power source 50 is electrically connected with the electrode layer 20, and a second end of the external power source 50 is electrically connected with a pen tip of the electronic pen 60.
As shown in fig. 2a, the first terminal of the external power source 50 is a positive electrode, and the second terminal of the external power source 50 is a negative electrode, wherein the voltage value of the external power source 50 is-1.5 v. When the tip of the electronic pen 60 is in contact with the electrolyte layer 40 on the second electrochromic layer 302, the potential of the electrolyte layer 40 is higher than that of the electrode layer 20, electrons move from a low potential to a high potential, so that the ferrous ions of the second electrochromic layer 302 undergo an oxidation-reduction reaction, lose electrons and become ferric ions, and thus an absorption peak is changed, thereby displaying blue.
As shown in fig. 2b, the first terminal of the external power source 50 is a positive terminal, and the second terminal of the external power source 50 is a negative terminal, wherein the voltage of the external power source 50 is-1.5 v. When the tip of the electronic pen 60 is in contact with the electrolyte layer 40 on the first electrochromic layer 301, the potential of the electrolyte layer 40 is higher than that of the electrode layer 20, electrons move from a low potential to a high potential, so that the divalent ruthenium ions of the first electrochromic layer 301 undergo a redox reaction, lose electrons and become trivalent ruthenium ions, and thus an absorption peak is changed, thereby displaying orange color.
Next, referring to fig. 3, a flowchart of a method for manufacturing an electrochromic display device according to an embodiment of the present invention is shown, where the method includes:
s1, providing a flexible substrate;
s2, preparing an electrode layer on the flexible substrate;
s3, preparing an electrochromic layer on the electrode layer, wherein the electrochromic layer comprises a plurality of first electrochromic layers and a plurality of second electrochromic layers which are distributed in an array, and the colors displayed by the first electrochromic layers and the second electrochromic layers are different after being electrified;
s4, preparing an electrolyte layer on the electrochromic layer.
It can be understood that, the embodiment of the present invention may implement an individually controlled multicolor display by dividing the electrochromic layer into a plurality of first electrochromic layers and a plurality of second electrochromic layers distributed in an array, individually controlling the above-mentioned color change of the energized electrochromic layers by individually energizing one of the electrochromic layers, and displaying different colors after energizing the first electrochromic layers and the second electrochromic layers.
In one embodiment, the first electrochromic layer and the second electrochromic layer are a conjugated polymer containing a divalent ruthenium ion and a conjugated polymer containing a ferrous ion, respectively, and the step S3 includes: and respectively dissolving the conjugated polymer containing the divalent ruthenium ions and the conjugated polymer containing the ferrous ions in deionized water to prepare a first electrochromic layer 301 aqueous solution and a second electrochromic layer 302 aqueous solution, wherein the mass fraction ratio of the conjugated polymer containing the divalent ruthenium ions and the conjugated polymer containing the ferrous ions to the deionized water is in the range of 1: [80, 150 ].
In one embodiment, the step S3 further includes: and respectively preparing the first electrochromic layer aqueous solution and the second electrochromic layer aqueous solution on the electrode layer by adopting an ink-jet printing process, and baking to form a plurality of first electrochromic layers and a plurality of second electrochromic layers which are distributed in an array manner.
In one embodiment, the step S4 includes:
preparing a mixed solution of polyvinylidene fluoride, dimethylformamide and nanocellulose crystal, wherein the mass fraction ratio of the polyvinylidene fluoride, the dimethylformamide and the nanocellulose crystal is 100: [400, 800]: [5, 10 ];
applying the mixed solution on the electrochromic layer to form a conductive film;
an ionic liquid electrolyte or a lithium gel electrolyte is applied on the conductive film to form an electrolyte membrane.
It should be noted that dimethylformamide is a transparent liquid, can be mutually soluble with water and most organic solvents, and is a common solvent for chemical reactions.
Specifically, referring to fig. 4a to 4e, which are schematic diagrams of basic structures of components in a manufacturing process of an electrochromic display device according to an embodiment of the present invention, first, as shown in fig. 4a, a flexible substrate 10 is prepared, where the flexible substrate 10 may be made of polyethylene terephthalate, the size of the flexible substrate 10 may be 8 × 8 cm, and the thickness of the flexible substrate 10 may be 1 to 2 mm; and then preparing an electrode layer 20 on the flexible substrate 10, wherein the effective area of the electrode layer 20 is 6 x 6 cm, and the thickness of the electrode layer 20 is 800-1500 angstroms.
Next, as shown in fig. 4b, preparing an aqueous solution of the electrochromic layer 30, specifically, dissolving a conjugated polymer containing divalent ruthenium ions and a conjugated polymer containing ferrous ions in deionized water, respectively, to prepare an aqueous solution of the first electrochromic layer 301 and an aqueous solution of the second electrochromic layer 302, wherein the mass fraction ratio of the conjugated polymer containing divalent ruthenium ions and the conjugated polymer containing ferrous ions to the deionized water is in the range of 1: [80, 150 ]; then, respectively performing inkjet printing on the first electrochromic layer 301 aqueous solution and the second electrochromic layer 302 aqueous solution on the electrode layer 20 to form patterns with the size of 1 × 1 cm, specifically, the patterns of the first electrochromic layer 301 aqueous solution are arranged corresponding to odd columns, the patterns of the second electrochromic layer 302 aqueous solution are arranged corresponding to even columns, the interval between any two adjacent patterns is 0.2-0.3 mm, in other embodiments, the patterns of the second electrochromic layer 302 aqueous solution may be arranged around the patterns of the first electrochromic layer 301 aqueous solution, that is, the patterns of the first electrochromic layer 301 aqueous solution and the patterns of the second electrochromic layer 302 aqueous solution in any row or any column are alternately arranged; and then, baking the substrate for 20 to 40 minutes by adopting a heat source at the temperature of 50 to 80 ℃, and obtaining a plurality of first electrochromic layers 301 and a plurality of second electrochromic layers 302 which are distributed in an array manner after baking.
Next, as shown in fig. 4c, preparing a mixed solution of polyvinylidene fluoride and nanocellulose crystal, specifically, adding polyvinylidene fluoride into dimethylformamide, and then adding nanocellulose crystal into the mixed solution of polyvinylidene fluoride and dimethylformamide, wherein the mass fraction ratio of polyvinylidene fluoride, dimethylformamide and nanocellulose crystal is in the range of 100: [400, 800]: [5, 10 ]; then preparing the mixed solution of the polyvinylidene fluoride, the dimethylformamide and the nanocellulose crystal on the electrochromic layer 30 by adopting an ink-jet printing process, and printing the mixed solution into patterns with the size of 1 × 1 cm, wherein the interval between any two adjacent patterns is 0.2-0.3 mm; and then, baking the substrate for 60 to 90 minutes by adopting a heat source at the temperature of 50 to 80 ℃, and drying to obtain the conductive film 401.
Next, as shown in FIG. 4d, an ionic liquid electrolyte (e.g., 1-ethyl-3-methylimidazolium bis (fluoromethylsulfonyl) imide (EMBTI)) or a lithium gel electrolyte (e.g., lithium perchlorate-polymethyl methacrylate-propylene carbonate (LiClO)4-PMMA-PC), lithium perchlorate-perchloric acid-polymethyl methacrylate-propylene carbonate (LiClO)4-HClO4PMMA-PC)) is prepared on the conductive film 401 using an inkjet printing process; and baking by adopting a heat source at 50-80 ℃ for 20-40 minutes to obtain an electrolyte membrane 402 after baking, wherein the electrolyte membrane 40 is formed by the conductive film 401 and the electrolyte membrane 402.
Finally, as shown in fig. 4e, the first end of the external power source 50 is electrically connected to the electrode layer 20, and the second end of the external power source 50 is electrically connected to the tip of the electronic pen 60, so that the electrochromic display device can be manufactured.
In one embodiment, the first terminal of the external power source 50 is a positive terminal, the second terminal of the external power source 50 is a negative terminal, and the voltage of the external power source 50 is-1.5 volts. In other embodiments, the first terminal of the external power source 50 may be a negative terminal, the second terminal of the external power source 50 may be a positive terminal, and the voltage value of the external power source 50 is 1.5 v.
In one embodiment, the external power source 50 and the electronic pen 60 are integrally formed, i.e., the external power source 50 can be embedded in the electronic pen 60.
In summary, an electrochromic display device provided in an embodiment of the present invention includes: the flexible substrate, be located the electrode layer on the flexible substrate, be located the electrochromic layer on the electrode layer and be located the electrolyte layer on the electrochromic layer, wherein, the electrochromic layer includes a plurality of first electrochromic layers and a plurality of second electrochromic layers that the array distributes, and the colour that shows is different after first electrochromic layer and second electrochromic layer circular telegram. According to the invention, the electrochromic layer is divided into the plurality of first electrochromic layers and the plurality of second electrochromic layers which are distributed in an array manner, the colors displayed after the first electrochromic layers and the second electrochromic layers are electrified are different, and the color development units can be controlled independently by electrifying the different electrochromic layers, so that the purpose of different color development is achieved, the controllable multi-color electrochromic display effect is realized, and the technical problems that the electrochromic display device in the prior art can only display one color, the potential change of the whole display device is consistent, and the color development units cannot be controlled independently are solved.
The electrochromic display device and the method for manufacturing the same according to the embodiments of the present invention are described in detail above. It should be understood that the exemplary embodiments described herein should be considered merely illustrative for facilitating understanding of the method of the present invention and its core ideas, and not restrictive.
Claims (10)
1. An electrochromic display device, characterized by comprising:
a flexible substrate;
an electrode layer located over the flexible substrate;
an electrochromic layer located over the electrode layer;
an electrolyte layer over the electrochromic layer;
the electrochromic layer comprises a plurality of first electrochromic layers and a plurality of second electrochromic layers which are distributed in an array mode, and the colors displayed by the first electrochromic layers and the second electrochromic layers after being electrified are different.
2. The electrochromic display device according to claim 1, wherein the first electrochromic layer and the second electrochromic layer are a conjugated polymer containing a divalent ruthenium ion and a conjugated polymer containing a ferrous ion, respectively.
3. The electrochromic display device according to claim 2, wherein said conjugated polymer containing a divalent ruthenium ion and said conjugated polymer containing a ferrous ion have respective molecular formulas
4. The electrochromic display device according to claim 1, wherein the electrolyte layer comprises a conductive film on a surface of the electrochromic layer on a side away from the electrode layer and an electrolyte film on a surface of the conductive film on a side away from the electrochromic layer.
5. The electrochromic display device according to claim 4, wherein a material of the conductive film is a mixture of polyvinylidene fluoride and nanocellulose crystal, and a material of the electrolyte film is an ionic liquid electrolyte or a lithium gel electrolyte.
6. The electrochromic display device according to claim 4 wherein said electrolyte layer has an electrical conductivity of greater than or equal to 4.0 milliSiemens per centimeter and less than or equal to 4.5 milliSiemens per centimeter.
7. The electrochromic display device according to claim 1, further comprising an external power source, a first end of the external power source being electrically connected to the electrode layer, a second end of the external power source being electrically connected to a nib of an electronic pen.
8. A method for manufacturing an electrochromic display device, comprising the steps of:
s1, providing a flexible substrate;
s2, preparing an electrode layer on the flexible substrate;
s3, preparing an electrochromic layer on the electrode layer, wherein the electrochromic layer comprises a plurality of first electrochromic layers and a plurality of second electrochromic layers which are distributed in an array, and the colors displayed by the first electrochromic layers and the second electrochromic layers are different after being electrified;
s4, preparing an electrolyte layer on the electrochromic layer.
9. The method of manufacturing an electrochromic display device according to claim 8, wherein the first electrochromic layer and the second electrochromic layer are a conjugated polymer containing a divalent ruthenium ion and a conjugated polymer containing a ferrous ion, respectively, and the step S3 includes:
and respectively dissolving the conjugated polymer containing divalent ruthenium ions and the conjugated polymer containing ferrous ions in deionized water to prepare a first electrochromic layer aqueous solution and a second electrochromic layer aqueous solution, wherein the mass fraction ratio of the conjugated polymer containing divalent ruthenium ions and the conjugated polymer containing ferrous ions to the deionized water is in the range of 1: [80, 150 ].
10. The method of manufacturing an electrochromic display device according to claim 8, wherein the step S4 includes:
preparing a mixed solution of polyvinylidene fluoride, dimethylformamide and nanocellulose crystal, wherein the mass fraction ratio of the polyvinylidene fluoride, the dimethylformamide and the nanocellulose crystal is 100: [400, 800]: [5, 10 ];
applying the mixed solution on the electrochromic layer to form a conductive film;
an ionic liquid electrolyte or a lithium gel electrolyte is applied on the conductive film to form an electrolyte membrane.
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