CN113253533A - Flexible electrochromic device and preparation method thereof - Google Patents

Flexible electrochromic device and preparation method thereof Download PDF

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CN113253533A
CN113253533A CN202110438068.8A CN202110438068A CN113253533A CN 113253533 A CN113253533 A CN 113253533A CN 202110438068 A CN202110438068 A CN 202110438068A CN 113253533 A CN113253533 A CN 113253533A
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layer
flexible
electrochromic device
flexible substrate
buffer medium
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CN113253533B (en
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邢爱
刘伟峰
侯丽新
臧美秀
刘贤豪
黄达
王亚丽
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China Lucky Group Corp
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China Lucky Group Corp
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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
    • G02F1/1523—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 inorganic material
    • G02F1/1525—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 inorganic material characterised by a particular ion transporting layer, e.g. electrolyte
    • 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
    • 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
    • G02F1/1523—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 inorganic material
    • 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
    • G02F1/1533—Constructional details structural features not otherwise provided for

Abstract

The invention discloses a flexible electrochromic device and a preparation method thereof, wherein the flexible electrochromic device comprises: the flexible substrate of first flexible substrate, first conducting layer, electrochromic layer, quasi solid electrolyte layer, ion storage layer, second conducting layer and the flexible substrate of second that the stromatolite set up in proper order still including setting up the buffer dielectric layer of at least one side on quasi solid electrolyte layer. The flexible electrochromic device is provided with the buffer medium layer on at least one side of the quasi-solid electrolyte layer, and the buffer medium layer can adsorb water, so that the influence of water on the flexible electrochromic device in the preparation and use processes of the flexible electrochromic device is prevented, the quality of the flexible electrochromic device and the humidity and heat resistance and other aging performances are improved, and the actual service life of the device is prolonged.

Description

Flexible electrochromic device and preparation method thereof
Technical Field
The invention belongs to the technical field of electrochromism, and particularly relates to a flexible electrochromism device and a preparation method thereof.
Background
The electrochromic is a reversible change of color and transparency of a material caused by oxidation-reduction reaction of the material through an electrochemical process under the action of an external electric field or current, and the change is caused by stable reversible change of optical properties (transmissivity, reflectivity or absorptivity) of the material in ultraviolet, visible or near-infrared regions under the action of the external electric field.
With the wide application of electrochromic devices, hard electrochromic devices cannot meet actual requirements, and flexible electrochromic devices with uniform preparation and excellent performance become important research directions of researchers. The flexible electrochromic device can dynamically adjust and control the optical properties (reflectivity, transmissivity, absorptivity and the like) of sunlight, has good bending performance and wide application range, and belongs to the fields of wearable equipment, flexible display and the like.
The basic structure of the electrochromic device is formed by combining a transparent substrate, a transparent conducting layer, an electrochromic layer, an ion conducting layer, an ion storage layer and other multilayer structures. At present, the electrolyte layer of the flexible electrochromic device mainly adopts quasi-solid electrolyte, although the requirement of flexible application can be met, because the important component (lithium salt) of the quasi-solid electrolyte has the characteristic of easily absorbing water vapor, the quasi-solid electrolyte easily absorbs the water vapor in the preparation process and the assembly process of the flexible electrochromic device, the service life of a functional layer of the electrochromic device is influenced, in addition, in the circulation process, bubbles are easily generated on the appearance of the device due to the existence of water, the service life of the electrochromic device is seriously influenced in the two aspects, and therefore, the application and popularization of the device are greatly limited.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to provide a flexible electrochromic device and a method for manufacturing the same. The flexible electrochromic device is provided with the buffer medium layer on at least one side of the quasi-solid electrolyte layer, and the buffer medium layer can adsorb water, so that the influence of water on the flexible electrochromic device in the preparation and use processes of the flexible electrochromic device is prevented, the quality of the flexible electrochromic device and the humidity and heat resistance and other aging performances are improved, and the actual service life of the device is prolonged.
In one aspect of the present invention, the present invention provides a flexible electrochromic device, according to an embodiment of the present invention, including:
the flexible substrate of first flexible substrate, first conducting layer, electrochromic layer, quasi solid electrolyte layer, ion storage layer, second conducting layer and the flexible substrate of second that the stromatolite set up in proper order still including setting up the buffer dielectric layer of at least one side on quasi solid electrolyte layer.
According to the flexible electrochromic device provided by the embodiment of the invention, the buffer medium layer is arranged on at least one side of the quasi-solid electrolyte layer, so that water vapor introduced in the preparation process of the quasi-solid electrolyte and the assembly process of the flexible electrochromic device can be effectively adsorbed, the quasi-solid electrolyte and the electrochromic layer are prevented from being damaged by the water vapor, the quality, the humidity and heat resistance and other aging properties of the flexible electrochromic device are improved, and the actual service life of the flexible electrochromic device is effectively prolonged.
In addition, the flexible electrochromic device according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the flexible electrochromic device comprises: the plasma display panel comprises a first flexible substrate, a first conducting layer, an electrochromic layer, a first buffer medium layer, a quasi-solid electrolyte layer, a second buffer medium layer, an ion storage layer, a second conducting layer and a second flexible substrate which are sequentially stacked.
In some embodiments of the present invention, the material of the buffer dielectric layer is an inorganic compound.
In some embodiments of the invention, the inorganic compound is selected from at least one of tantalum pentoxide, silicon oxide, chromium oxide, zirconium oxide, hafnium oxide, magnesium fluoride, calcium fluoride, and barium fluoride.
In some embodiments of the present invention, the thickness of the buffer dielectric layer is 50-200 nm.
In some embodiments of the invention, the buffer dielectric layer is a loose porous structure film, thereby not blocking Li+The water absorbed by the buffer medium layer participates in the oxidation-reduction reaction of the electrochromic layer under an external electric field, and the color changing speed of the electrochromic device is accelerated, so that the flexible electrochromic device has a wider color changing range under low voltage.
In some embodiments of the present invention, the preparation method of the buffer dielectric layer is a direct current magnetron reactive sputtering method or an electron beam method.
In some embodiments of the invention, during the preparation of the buffer medium layer, the coating speed is less than 0.5 nm/s.
In some embodiments of the present invention, the base film temperature is less than 50 ℃ during the preparation of the buffer dielectric layer.
In some embodiments of the present invention, the material of the quasi-solid electrolyte layer includes a resin host, a plasticizer, a lithium salt, nano inorganic particles, and an auxiliary agent.
In some embodiments of the present invention, the resin body is selected from at least one of polyoxyethylene ether, polyvinylidene fluoride, polymethyl methacrylate, and polyvinyl butyral.
In some embodiments of the invention, the plasticizer is selected from at least one of ethylene carbonate, propylene carbonate, ethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
In some embodiments of the invention, the lithium salt is selected from at least one of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, and lithium bis (pentafluoroethylsulfonyl) imide.
In some embodiments of the present invention, the material of the first flexible substrate and the material of the second flexible substrate are each independently selected from at least one of polyethylene terephthalate, polyethylene naphthalate, and polyimide.
In some embodiments of the present invention, the thickness of the first flexible substrate is 100-.
In some embodiments of the present invention, the thickness of the second flexible substrate is 100-.
In some embodiments of the present invention, the material of the first conductive layer and the material of the second conductive layer are each independently selected from at least one of tin-doped indium oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide.
In some embodiments of the present invention, the material of the electrochromic layer is selected from at least one of tungsten oxide, molybdenum oxide, niobium pentoxide, and titanium dioxide.
In some embodiments of the present invention, the electrochromic layer has a thickness of 300-600 nm.
In some embodiments of the invention, the material of the ion storage layer is selected from at least one of nickel oxide, iridium oxide and manganese oxide.
In some embodiments of the present invention, the thickness of the ion storage layer is 200-450 nm.
In yet another aspect of the invention, the invention provides a method of making the above-described flexible electrochromic device. According to an embodiment of the invention, the method comprises:
sequentially preparing a first conductive layer, an electrochromic layer and a first buffer medium layer on the surface of a first flexible substrate so as to obtain a first composite layer; sequentially preparing a second conducting layer, an ion storage layer and a second buffer medium layer on the surface of a second flexible substrate so as to obtain a second composite layer; sequentially carrying out roll-to-roll hot-pressing compounding on the first composite layer, the quasi-solid electrolyte layer and the second composite layer so as to obtain a flexible electrochromic device;
or a first conductive layer, an electrochromic layer and a first buffer medium layer are sequentially prepared on the surface of the first flexible substrate so as to obtain a first composite layer; sequentially preparing a second conductive layer and an ion storage layer on the surface of a second flexible substrate so as to obtain a second composite layer; sequentially carrying out roll-to-roll hot-pressing compounding on the first composite layer, the quasi-solid electrolyte layer and the second composite layer so as to obtain a flexible electrochromic device;
or a first conductive layer and an electrochromic layer are sequentially prepared on the surface of the first flexible substrate so as to obtain a first composite layer; sequentially preparing a second conducting layer, an ion storage layer and a second buffer medium layer on the surface of a second flexible substrate so as to obtain a second composite layer; and sequentially carrying out roll-to-roll hot-pressing compounding on the first composite layer, the quasi-solid electrolyte layer and the second composite layer so as to obtain the flexible electrochromic device.
According to the method for preparing the flexible electrochromic device, the buffer medium layer is prepared on at least one side of the quasi-solid electrolyte layer, so that water vapor introduced in the preparation process of the quasi-solid electrolyte and the assembly process of the flexible electrochromic device can be effectively adsorbed, the quasi-solid electrolyte and the electrochromic layer are prevented from being damaged by the water vapor, the quality, the humidity and heat resistance and other aging performances of the flexible electrochromic device are improved, and the actual service life of the flexible electrochromic device is effectively prolonged. On the other hand, by the method, each functional layer of the flexible electrochromic device can be independently prepared, and each process is more conveniently and accurately controlled, so that the production efficiency and the product yield of the flexible electrochromic device are improved; in addition, the preparation method has wide requirements on the preparation environment of each functional layer, can be carried out in a low dew point environment, is simple and quick to operate, and can greatly reduce the production cost.
Compared with the prior art, the invention has the beneficial effects that:
(1) because the important component (lithium salt) of the quasi-solid electrolyte has the characteristic of easy water vapor absorption, the quasi-solid electrolyte is easy to absorb the water vapor in the preparation process and the assembly process of the flexible electrochromic device, and the service life of a functional layer of the electrochromic device is influencedEffectively prolonging the actual service life of the flexible electrochromic device. Meanwhile, during the coloring and discoloring process (voltage application) of the device, water can also be decomposed, and decomposed H+Can participate in the oxidation-reduction reaction of the electrochromic layer, and the buffer medium layer is used as OH-The ion storage layer accelerates the color changing speed of the electrochromic device, so that the flexible electrochromic device reaches the final saturation state of the device in a short time under low voltage.
(2) The buffer medium layer provided by the invention is of a loose porous structure, and when no water exists in the flexible electrochromic device system, the buffer medium layer does not block Li in the electrolyte layer+Does not affect the fading properties of the flexible electrochromic device.
(3) According to the preparation method of the flexible electrochromic device, each functional layer of the flexible electrochromic device can be independently prepared, and each process is more conveniently and accurately controlled, so that the production efficiency and the product yield of the flexible electrochromic device are improved; in addition, the preparation process has wide requirements on the preparation environment of the functional layer, can be carried out in a low dew point environment, is simple and quick to operate, and can greatly reduce the production cost.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic structural diagram of a flexible electrochromic device provided in an embodiment of the present invention;
in the figure, 1-a first flexible substrate, 2-a first conductive layer, 3-an electrochromic layer, 4-1-a first buffer dielectric layer, 5-a quasi-solid electrolyte layer, 4-2-a second buffer dielectric layer, 6-an ion storage layer, 7-a second conductive layer, and 8-a second flexible substrate.
Fig. 2 is a scanning electron microscope image of a loose porous structure of a buffer medium layer provided in embodiment 1 of the present invention.
Fig. 3 is a transmittance change spectrum of the flexible electrochromic device provided in embodiment 1 of the present invention during a color fading process.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the present invention, the present invention provides a flexible electrochromic device, which includes, according to an embodiment of the present invention, with reference to fig. 1: the flexible substrate comprises a first flexible substrate 1, a first conducting layer 2, an electrochromic layer 3, a quasi-solid electrolyte layer 5, an ion storage layer 6, a second conducting layer 7 and a second flexible substrate 8 which are sequentially stacked, and further comprises a buffer medium layer arranged on at least one side of the quasi-solid electrolyte layer 5. Therefore, the buffer medium layer is arranged on at least one side of the quasi-solid electrolyte layer 5, so that water vapor introduced in the preparation process of the quasi-solid electrolyte and the assembly process of the flexible electrochromic device can be effectively adsorbed, the quasi-solid electrolyte and the electrochromic layer 3 are prevented from being damaged by the water vapor, the quality, the humidity and heat resistance and other aging properties of the flexible electrochromic device are improved, and the actual service life of the flexible electrochromic device is effectively prolonged.
According to a specific embodiment of the present invention, referring to fig. 1, the flexible electrochromic device includes: the plasma display panel comprises a first flexible substrate 1, a first conducting layer 2, an electrochromic layer 3, a first buffer medium layer 4-1, a quasi-solid electrolyte layer 5, a second buffer medium layer 4-2, an ion storage layer 6, a second conducting layer 7 and a second flexible substrate 8 which are sequentially stacked.
According to yet another embodiment of the present invention, the buffer dielectric layer is a loose porous structure thin film, thereby not blocking Li+And the water absorbed by the buffer medium layer participates in the oxidation-reduction reaction of the electrochromic layer 3 under an applied electric field, so that the change of the electrochromic device is acceleratedColor speed, thereby enabling the flexible electrochromic device to have a wider color change range at low voltage. Specifically, the adsorbed water is decomposed under an applied electric field to generate H+And OH-，H+Can be injected into the electrochromic layer 3 with electrons from the electrode to perform oxidation-reduction reaction to realize color change, and the buffer medium layer is used as OH-The ion storage layer 6. This process and Li+The redox reactions of the electrochromic layer 3 which participate as the conduction ions are superposed, so that the flexible electrochromic device realizes rapid color change and reaches a saturated state. When a reverse voltage is applied, H+Is extracted from the electrochromic layer 3 and returns to the buffer medium layer to react with OH-Water is produced by the reaction again, while Li+And returning to the ion storage layer 6, carrying out oxidation-reduction reaction, and realizing color fading of the flexible electrochromic device. Therefore, in the coloring and fading process of the flexible electrochromic device, H is generated+And Li+Simultaneously, the reaction is participated, so that the color changing speed of the electrochromic device can be greatly accelerated, and the flexible electrochromic device can reach the final saturation state of the flexible electrochromic device in a short time under low voltage.
In an embodiment of the present invention, the above Li+The specific process of the redox reaction of the electrochromic layer 3 participating as a conductive ion is as follows: electrons enter the electrochromic layer from the negative electrode, but it cannot pass through the insulating electrolyte layer and then enter the ion storage layer, and lithium ions enter the electrochromic layer from the ion storage layer side through the electrolyte layer, the device starts coloring, and the visible light transmittance decreases. After a reverse voltage is applied, lithium ions are extracted from the electrochromic layer film and return to the ion storage layer, electrons return to the anode from the electrochromic layer, cathode electrons enter the ion storage layer and are neutralized with the ions, the electroneutrality is kept, the color of the device returns to a transparent state, and the process is called 'bleaching'. If the ion storage layer of the device also uses electrochromic material as the counter electrode layer, the two counter electrode films have different coloring and fading conditions, and the ion storage layer or the counter electrode which are opposite in the device have complementary characteristics, so that the method is considered to be preferable, for example, the electrochromic material is attached as a cathodeWhen the device is colored, the anode coloring material is used as the counter electrode, so that the cathode and the anode can be simultaneously colored or faded under the action of an applied voltage, the color of the device in a colored state is deepened, and the lower transmittance in the colored state is obtained. The device thus assembled is called a complementary electrochromic device. When the complementary device is colored and faded, the cathode and the anode react at the same time, and when the reaction is carried out in the forward direction, the cathode and the anode react at the same time to color the device; when the reverse process is carried out, the cathode and the anode react simultaneously, and the device fades. The reaction formula is as follows:
cathode:
Figure BDA0003033962360000061
wherein MO isyBeing colourless, LixMOyM is usually W, Mo, V, Nb, etc., for coloring.
Anode:
Figure BDA0003033962360000062
wherein MO isyBeing colourless, LixMOyM is usually Ni, Ir, Rh, Co, etc., for coloring.
According to another embodiment of the invention, the preparation method of the buffer dielectric layer is a direct current magnetron reactive sputtering method or an electron beam method.
According to another embodiment of the invention, the buffer medium layer with a loose porous structure can be prepared by controlling the sputtering speed, the oxygen flux and the temperature of the base film in the preparation process. The inventor finds that in the preparation process of the buffer dielectric layer, the lower coating speed, the lower base film temperature and the sufficient oxygen flux are beneficial to forming a loose and porous buffer dielectric layer structure. Specifically, if the coating speed is controlled to be less than 0.5nm/s (e.g., 0.4nm/s, 0.3nm/s, 0.2nm/s, 0.1nm/s, etc.), the formed crystal grains are large, the structure of the film layer is loose and porous, and an excessively high coating speed causes fine crystal grains and a compact structure of the film layer, which are not favorable for conducting ions, thereby affecting the color change speed and the coloring efficiency of the flexible electrochromic device, and therefore, in the preparation process of the buffer medium layer, the coating speed should be less than 0.5 nm/s. Controlling the temperature of the base membrane to be less than 50 ℃ (such as 40 ℃, 30 ℃, 20 ℃, 10 ℃ and the like), wherein the formed membrane is amorphous and has a loose and porous structure; and too high base film temperature can cause the compact structure of the film layer, is easy to crystallize and has certain influence on the color changing speed of the electrochromic device, so that the base film temperature is less than 50 ℃ in the preparation process of the buffer dielectric layer. In addition, a certain amount of oxygen is introduced in the preparation process of the buffer dielectric layer, so that a loose porous structure is formed.
According to the embodiment of the present invention, the specific type of the material of the buffer medium layer is not particularly limited, and one skilled in the art may optionally select the material according to actual needs, and as a preferable scheme, the material of the buffer medium layer is an inorganic compound. Further, the inorganic compound is selected from tantalum pentoxide (Ta)2O5) Silicon oxide (SiO)x) Chromium oxide (Cr)2O3) Zirconium oxide (ZrO)2) Hafnium oxide (HfO)2) Magnesium fluoride (MgF)2) Calcium fluoride (CaF)2) And barium fluoride (BaF)2) Therefore, the inorganic compound material has strong water adsorption performance, can adsorb water in the assembly and use processes of the flexible electrochromic device, prevents the water from damaging the quasi-solid electrolyte and the electrochromic layer 3, improves the quality of the flexible electrochromic device and the aging performance such as heat and humidity resistance, and effectively prolongs the actual service life of the flexible electrochromic device; meanwhile, the inorganic compound material has higher refractive index, higher dielectric constant and chemical stability, and can be used for preparing a film with good light transmittance without influencing the light transmittance and the regulation and control amplitude of the flexible electrochromic device by controlling the proper thickness.
According to another embodiment of the present invention, the thickness of the buffer medium layer is 50-200nm (e.g. 50nm, 100nm, 150nm, 200nm, etc.), and the inventors found that if the thickness of the buffer medium layer is less than 50nm, the adsorption capacity for water is insufficient; in order to increase the water adsorption amount of the buffer medium layer, the thickness of the buffer medium layer needs to be further increased, but if the thickness is larger than 200nm, although the light transmittance of the flexible electrochromic device is not greatly influenced, the cost of the device can be increased, and therefore, the thickness of the buffer medium layer is more suitable for 50nm-200 nm.
According to the embodiment of the invention, the quasi-solid electrolyte has the advantages of low cost, easy processing and synthesis, good durability, very high transparency and the like. The quasi-solid electrolyte is used as an ion conduction medium between the electrochromic layer 3 and the ion storage layer 6, and is required to have the characteristics of high ionic conductivity, wide electrochemical window, high optical transparency, chemical and electrochemical stability and the like. The quasi-solid electrolyte is a two-phase system formed by distributing an ionic conductor medium in a polymer matrix, and due to the unique mixed network structure, the gel has solid cohesiveness and liquid diffusion and transmission characteristics. The quasi-solid electrolyte is formed by dissolving one or more lithium salts in one or more solvents, coating the solution on a release material by a slot coating or blade coating method, and removing the solvent.
According to yet another embodiment of the present invention, the material of the quasi-solid electrolyte layer 5 includes a resin host, a plasticizer, a lithium salt, nano inorganic particles, and an auxiliary agent. The polymer resin main body plays a supporting role in the quasi-solid electrolyte on one hand, so that the electrolyte does not flow, and the device packaging is facilitated; on the other hand, the structural unit of the polyether chain segment contains an ether oxygen side bond, the polyether chain segment can perform solvation with inorganic lithium salt, and along with the movement of the polymer chain segment, the ether oxygen group in the polyether chain segment can perform complexation-decomplexing with the inorganic lithium salt to promote the transmission of charged particles in a polymer matrix. In addition, the polymers are stable, and a large electrochemical window can be obtained, so that a guarantee is provided for the application process of the flexible electrochromic device. Lithium salt is an important constituent of the electrolyte and can provide Li for the electrochromic layer 3 to change color+Ions, which require better solubility and dissociation ability in the plasticizer. The ionic plasticizer is a good solvent of lithium salt, and is a carrier of the lithium salt in the quasi-solid electrolyte, so that the glass transition temperature of the PVB resin can be further adjusted, the mobility of the polymer chain segment is improved, and the carrier moving along with the polymer chain segment is facilitatedThe transportation of (3); through the intermolecular interaction between the dipoles and the polymers, the polarities of the polymers and the polarities of the polymers are improved, and the dissociation of lithium salts in a polymer electrolyte is promoted; the coordination bond between the lithium ion and the polymer is broken, so that more lithium ions move in a gel state rather than a crystal phase, thereby improving the ionic conductivity of the quasi-solid electrolyte. The addition of chemical substances such as nano inorganic particles, auxiliaries and the like provides some guarantee for the ionic conductivity and stability of the quasi-solid electrolyte.
In the embodiment of the present invention, the specific kind of the material of the above resin body is not particularly limited, and may be arbitrarily selected by those skilled in the art according to actual needs, and as a preferable embodiment, the resin body is selected from at least one of Polyoxyethylene Ether (PEO), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), and polyvinyl butyral (PVB).
In the embodiment of the present invention, the specific kind of the material of the plasticizer is not particularly limited, and may be arbitrarily selected by those skilled in the art according to actual needs, and as a preferable embodiment, the plasticizer is at least one selected from the group consisting of ethylene carbonate, propylene carbonate, ethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
In the embodiment of the present invention, the specific kind of the material of the lithium salt is not particularly limited, and may be arbitrarily selected by those skilled in the art according to actual needs, and as a preferable embodiment, the lithium salt is at least one selected from the group consisting of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, and lithium bis (pentafluoroethylsulfonyl) imide.
In the embodiment of the present invention, the specific kind of the material of the first flexible substrate 1 is not particularly limited, and may be arbitrarily selected by those skilled in the art according to actual needs, and as a preferable scheme, the material of the first flexible substrate 1 is at least one selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and Polyimide (PI).
In the embodiment of the present invention, the specific kind of the material of the second flexible substrate 8 is not particularly limited, and may be arbitrarily selected by those skilled in the art according to actual needs, and as a preferable scheme, the material of the second flexible substrate 8 is at least one selected from polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and Polyimide (PI).
According to another embodiment of the present invention, the thickness of the first flexible substrate 1 is 100-180 μm, and the transmittance is greater than 88%.
According to another embodiment of the present invention, the thickness of the second flexible substrate 8 is 100-180 μm, and the transmittance is greater than 88%.
In the embodiment of the present invention, the specific kind of the material of the first conductive layer 2 is not particularly limited, and may be arbitrarily selected by those skilled in the art according to actual needs, and as a preferable scheme, the material of the first conductive layer 2 is selected from at least one of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), and aluminum-doped zinc oxide (AZO). The resistance of the first conductive layer 2 is less than 60 Ω/□.
In the embodiment of the present invention, the specific kind of the material of the second conductive layer 7 is not particularly limited, and may be arbitrarily selected by those skilled in the art according to actual needs, and as a preferable scheme, the material of the second conductive layer 7 is selected from at least one of tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), and aluminum-doped zinc oxide (AZO). The resistance of the second conductive layer 7 is less than 60 Ω/□.
In the embodiment of the present invention, the specific kind of the material of the electrochromic layer 3 is not particularly limited, and may be arbitrarily selected by those skilled in the art according to actual needs, and as a preferable scheme, the material of the electrochromic layer 3 is selected from tungsten oxide (WO)3) Molybdenum oxide (MoO)3) Niobium pentoxide (Nb)2O5) And titanium dioxide (TiO)2) At least one of (a).
According to another embodiment of the present invention, the electrochromic layer 3 is prepared by evaporation (vacuum or electron beam), sputtering, chemical vapor deposition, etc. with a thickness of 300-600 nm.
In the embodiment of the present invention, the above-described material of the ion storage layer 6 is specificallyThe kind is not particularly limited, and those skilled in the art can freely select the ion storage layer according to actual needs, and as a preferable scheme, the material of the ion storage layer 6 is selected from nickel oxide (NiO)x) Iridium oxide (Ir)2O3) And manganese oxide (MnO)2) At least one of (a).
According to another embodiment of the present invention, the ion storage layer 6 is prepared by evaporation (vacuum or electron beam), sputtering, chemical vapor deposition, or the like, and has a thickness of 200-450 nm.
In yet another aspect of the invention, the invention provides a method of making the above-described flexible electrochromic device. According to an embodiment of the invention, the method comprises:
sequentially preparing a first conductive layer 2, an electrochromic layer 3 and a first buffer medium layer 4-1 on the surface of a first flexible substrate 1 so as to obtain a first composite layer; a second conducting layer 7, an ion storage layer 6 and a second buffer medium layer 4-2 are sequentially prepared on the surface of a second flexible substrate 8 so as to obtain a second composite layer; sequentially carrying out roll-to-roll hot-pressing compounding on the first composite layer, the quasi-solid electrolyte layer 5 and the second composite layer so as to obtain a flexible electrochromic device;
or a first conducting layer 2, an electrochromic layer 3 and a first buffer medium layer 4-1 are sequentially prepared on the surface of the first flexible substrate 1 so as to obtain a first composite layer; sequentially preparing a second conductive layer 7 and an ion storage layer 6 on the surface of a second flexible substrate 8 so as to obtain a second composite layer; sequentially carrying out roll-to-roll hot-pressing compounding on the first composite layer, the quasi-solid electrolyte layer 5 and the second composite layer so as to obtain a flexible electrochromic device;
or a first conductive layer 2 and an electrochromic layer 3 are sequentially prepared on the surface of the first flexible substrate 1 so as to obtain a first composite layer; a second conducting layer 7, an ion storage layer 6 and a second buffer medium layer 4-2 are sequentially prepared on the surface of a second flexible substrate 8 so as to obtain a second composite layer; and sequentially carrying out roll-to-roll hot-pressing compounding on the first composite layer, the quasi-solid electrolyte layer 5 and the second composite layer so as to obtain the flexible electrochromic device.
According to the embodiment of the invention, the flexible electrochromic device is assembled in a roll-to-roll hot-pressing compounding mode, wherein the compounding speed is 1-5 m/min, the hot-pressing temperature is 50-80 ℃, and the pressure is 0.15-0.3 MPa. Therefore, the composite device has good bonding performance, excellent device appearance and is not easy to have the defects of bubbles, displacement and the like.
According to the method for preparing the flexible electrochromic device, the buffer medium layer is prepared on at least one side of the quasi-solid electrolyte layer, so that water vapor introduced in the preparation process of the quasi-solid electrolyte and the assembly process of the flexible electrochromic device can be effectively adsorbed, the quasi-solid electrolyte and the electrochromic layer are prevented from being damaged by the water vapor, the quality, the humidity and heat resistance and other aging performances of the flexible electrochromic device are improved, and the actual service life of the flexible electrochromic device is effectively prolonged. On the other hand, by the method, each functional layer of the flexible electrochromic device can be independently prepared, and each process is more conveniently and accurately controlled, so that the production efficiency and the product yield of the flexible electrochromic device are improved; in addition, the preparation method has wide requirements on the preparation environment of each functional layer, can be carried out in a low dew point environment, is simple and quick to operate, and can greatly reduce the production cost.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
1. The flexible electrochromic device structure is as follows: referring to fig. 1, comprising: the plasma display panel comprises a first flexible substrate 1, a first conducting layer 2, an electrochromic layer 3, a first buffer medium layer 4-1, a quasi-solid electrolyte layer 5, a second buffer medium layer 4-2, an ion storage layer 6, a second conducting layer 7 and a second flexible substrate 8 which are sequentially stacked.
The material of the first flexible substrate and the second flexible substrate is polyethylene terephthalate (PET), the thickness is 125 μm, and the transmittance is 91%.
The first conducting layer and the second conducting layer are both tin-doped indium oxide (ITO) prepared by a magnetron sputtering method, and the resistance is 40 omega/□.
The electrochromic layer is tungsten oxide prepared by electron beam evaporation (WO)3) And the thickness is 450 nm.
The first buffer medium layer and the second buffer medium layer are both calcium fluoride (CaF)2) The film is prepared by an electron beam evaporation method, the thickness of the first buffer medium layer and the thickness of the second buffer medium layer are both 80nm, the film coating speed is 0.3nm/s, and the temperature of the base film is 25 ℃.
The ion storage layer is nickel oxide (NiO) prepared by electron beam evaporationx) And the thickness is 350 nm.
Fig. 2 is a scanning electron microscope image of the loose porous structure of the first buffer medium layer provided in example 1, and it can be seen from the image that the first buffer medium layer is a loose structure, and the structure does not affect the conduction of lithium ions and hydrogen ions, and does not affect the performance of the conventional electrochromic device. The second buffer medium layer is also a loose porous structure, and is not described in detail herein.
2. Steps for preparing flexible electrochromic device
Selecting a first flexible base material and a second flexible base material, and cleaning; depositing a first conductive layer 2, an electrochromic layer 3 and a first buffer medium layer 4-1 on the surface of a first flexible substrate 1 in sequence by adopting a coating process to obtain a first composite layer; depositing a second conducting layer 7, an ion storage layer 6 and a second buffer medium layer 4-2 on the surface of a second flexible substrate 8 in sequence to obtain a second composite layer; and performing roll-to-roll hot-pressing compounding on the first composite layer 4-1, the second composite layer 4-2 and the quasi-solid electrolyte layer 5 to obtain the flexible electrochromic device.
The assembly of the flexible electrochromic device is carried out in a drying room in a roll-to-roll hot-pressing compounding mode, wherein the compounding speed is 3 m/min; the temperature of the hot-pressing compounding is 70 ℃, and the pressure is 0.15 MPa.
3. Test and results
Device performance
The flexible electrochromic device is subjected to coloring and fading at-1.8V/1.5V, wherein the coloring response time is 56s, and the fading response time is 52 s; cycle stability performance: cycle 1000 times, no bubble is produced.
Double eight five aging
The flexible electrochromic device is placed at 85 ℃ and 85% RH, and after being stored for 100 hours, the flexible electrochromic device is colored and faded at-1.8V/1.5V, wherein the coloring response time is 30s, and the fading response time is 27s, which is shown in figure 3; cycle stability performance: cycle 1000 times, no bubble is produced.
Example 2
1. The flexible electrochromic device structure is as follows: referring to fig. 1, comprising: the plasma display panel comprises a first flexible substrate 1, a first conducting layer 2, an electrochromic layer 3, a first buffer medium layer 4-1, a quasi-solid electrolyte layer 5, a second buffer medium layer 4-2, an ion storage layer 6, a second conducting layer 7 and a second flexible substrate 8 which are sequentially stacked.
The first flexible substrate and the second flexible substrate are both Polyimide (PI) films, the thickness of the Polyimide (PI) films is 100 micrometers, and the transmittance of the Polyimide (PI) films is 89%.
The first conducting layer and the second conducting layer are both tin-doped indium oxide (ITO) prepared by a magnetron sputtering method, and the resistance is less than 35/□.
The electrochromic layer is titanium dioxide (TiO) prepared by adopting a magnetron sputtering method2) The thickness is 500 nm.
The first buffer medium layer is made of zirconium oxide (ZrO)2) The film is prepared by an electron beam evaporation method, the thickness is 80nm, the film coating speed is 0.3nm/s, and the base film temperature is 20 ℃.
The second buffer medium layer is made of calcium magnesium (MgF)2) The film is prepared by an electron beam evaporation method, the thickness is 100nm, the film coating speed is 0.2nm/s, and the base film temperature is 20 ℃.
The ion storage layer is prepared by preparing nickel oxide (NiO) by magnetron sputtering methodx) And the thickness is 250 nm.
2. Steps for preparing flexible electrochromic device
The device assembly procedure was the same as in example 1.
The assembly of the flexible electrochromic device is carried out in a drying room in a roll-to-roll hot-pressing compounding mode, wherein the compounding speed is 2 m/min; the temperature of the hot-pressing compounding is 60 ℃, and the pressure is 0.25 MPa.
3. Test and results
Device performance
The flexible electrochromic device is subjected to coloring and fading at-1.8V/1.5V, wherein the coloring response time is 52s, and the fading response time is 49 s; cycle stability performance: cycle 1000 times, no bubble is produced.
Double eight five aging
The flexible electrochromic device is placed at 85 ℃ and 85% RH, and after being stored for 100 hours, the flexible electrochromic device is colored and faded at-1.8V/1.5V, wherein the coloring response time is 35s, and the fading response time is 29 s; cycle stability performance: cycle 1000 times, no bubble is produced.
Example 3
1. The flexible electrochromic device has the following structure and composition: the device comprises a first flexible substrate, a first conducting layer, an electrochromic layer, a first buffer medium layer, a quasi-solid electrolyte layer, an ion storage layer, a second conducting layer and a second flexible substrate which are sequentially stacked.
The first flexible base material and the second flexible base material are both polyethylene naphthalate (PEN), the thickness is 150 micrometers, and the transmittance is 90%.
The first conducting layer and the second conducting layer are both fluorine-doped tin oxide (FTO) prepared by a magnetron sputtering method, and the resistance is 50 omega/□.
The electrochromic layer is tungsten oxide prepared by adopting a magnetron sputtering method (WO)3) The thickness is 500 nm.
The first buffer medium layer is made of tantalum pentoxide (Ta)2O5) The film is prepared by a magnetron reactive sputtering method, the thickness is 150nm, the film coating speed is 0.4nm/s, and the temperature of a basal film is 40 ℃.
The ion storage layer is nickel oxide (NiO) prepared by electron beam evaporationx) And the thickness is 400 nm.
2. Steps for preparing flexible electrochromic device
Selecting a first flexible base material and a second flexible base material, and cleaning; depositing a first conductive layer, an electrochromic layer and a first buffer medium layer on the surface of a first flexible substrate in sequence by adopting a coating process to obtain a first composite layer; depositing a second conducting layer and an ion storage layer on the surface of a second flexible substrate in sequence to obtain a second composite layer; and carrying out reel-to-reel hot-pressing compounding on the first composite layer, the second composite layer and the quasi-solid electrolyte layer to obtain the flexible electrochromic device.
The assembly of the flexible electrochromic device is carried out in a drying room by adopting a roll-to-roll hot-pressing compounding mode, wherein the compounding speed is 4 m/min; the temperature of the hot-pressing compounding is 50 ℃, and the pressure is 0.3 MPa.
3. Test and results
Device performance
The flexible electrochromic device is subjected to coloring and fading at-1.8V/1.5V, wherein the coloring response time is 59s, and the fading response time is 54 s; cycle stability performance: cycle 1000 times, no bubble is produced.
Double eight five aging
The flexible electrochromic device is placed at 85 ℃ and 85% RH, and after being stored for 100 hours, the flexible electrochromic device is colored and faded at-1.8V/1.5V, wherein the coloring response time is 36s, and the fading response time is 31 s; cycle stability performance: cycle 1000 times, no bubble is produced.
Example 4
1. The flexible electrochromic device has the following structure and composition: the ion storage device comprises a first flexible substrate, a first conducting layer, an electrochromic layer, a quasi-solid electrolyte layer, a second buffer medium layer, an ion storage layer, a second conducting layer and a second flexible substrate which are sequentially stacked.
The first flexible base material and the second flexible base material are both made of polyethylene terephthalate (PET), the thickness of the first flexible base material is 125 micrometers, and the transmittance of the first flexible base material is 91%.
The first conducting layer and the second conducting layer are both fluorine-doped tin oxide (FTO) prepared by a magnetron sputtering method, and the resistance is 50 omega/□.
The electrochromic layer is molybdenum oxide (MoO) prepared by adopting a magnetron sputtering method3) A thickness of500nm。
The material of the second buffer dielectric layer is barium fluoride (BaF)2) The film is prepared by an electron beam evaporation method, the thickness is 50nm, the film coating speed is 0.3nm/s, and the base film temperature is 40 ℃.
According to an embodiment of the present invention, the ion storage layer is iridium oxide (Ir) prepared by electron beam evaporation2O3) And the thickness is 350 nm.
2. Steps for preparing flexible electrochromic device
Selecting a first flexible base material and a second flexible base material, and cleaning; sequentially depositing a first conductive layer and an electrochromic layer on the surface of a first flexible substrate by adopting a coating process to obtain a first composite layer; depositing a second conducting layer, an ion storage layer and a second buffer medium layer on the surface of a second flexible substrate in sequence to obtain a second composite layer; and carrying out reel-to-reel hot-pressing compounding on the first composite layer, the second composite layer and the quasi-solid electrolyte layer to obtain the flexible electrochromic device.
The assembly of the flexible electrochromic device is carried out in a drying room in a roll-to-roll hot-pressing compounding mode, wherein the compounding speed is 3 m/min; the temperature of the hot-pressing compounding is 50 ℃, and the pressure is 0.3 MPa.
3. Test and results
Device performance
The flexible electrochromic device is subjected to coloring and fading at-1.8V/1.5V, wherein the coloring response time is 54s, and the fading response time is 48 s; cycle stability performance: cycle 1000 times, no bubble is produced.
Double eight five aging
The flexible electrochromic device is placed at 85 ℃ and 85% RH, and after being stored for 100 hours, the flexible electrochromic device is colored and faded at-1.8V/1.5V, wherein the coloring response time is 38s, and the fading response time is 35 s; cycle stability performance: after 766 cycles, bubble generation began.
Comparative example 1
1. The flexible electrochromic device has the following structure and composition: the method comprises the following steps: the device comprises a first flexible substrate, a first conducting layer, an electrochromic layer, a quasi-solid electrolyte layer, an ion storage layer, a second conducting layer and a second flexible substrate which are sequentially arranged.
Otherwise, the same procedure as in example 1 was repeated.
2. Steps for preparing flexible electrochromic device
Selecting a first flexible base material and a second flexible base material, and cleaning; sequentially depositing a first conductive layer and an electrochromic layer on the surface of a first flexible substrate by adopting a coating process to obtain a first composite layer; depositing a second conducting layer and an ion storage layer on the surface of a second flexible substrate in sequence to obtain a second composite layer; and carrying out reel-to-reel hot-pressing compounding on the first composite layer, the second composite layer and the quasi-solid electrolyte layer to obtain the flexible electrochromic device.
The assembly process of the flexible electrochromic device was the same as in example 1.
3. Test and results
Device performance
The flexible electrochromic device is subjected to coloring and fading at-1.8V/1.5V, wherein the coloring response time is 57s, and the fading response time is 55 s; cycle stability performance: after 558 cycles, bubble generation began.
Double eight five aging
The flexible electrochromic device is placed at 85 ℃ and 85% RH, and after being stored for 100 hours, the flexible electrochromic device is colored and faded at-1.8V/1.5V, wherein the coloring response time is 38s, and the fading response time is 35 s; cycle stability performance: x: the cycle times were < 50 times, and bubbles were generated.
Test and evaluation method
The flexible electrochromic device was colored and discolored by applying a voltage (-1.8V/1.5V) to the devices of examples 1 to 4 and comparative example 1, respectively, using chenhua electrochemical analysis, and the change of transmittance with time at a wavelength of 550nm was measured by an ultraviolet-visible spectrophotometer, and the time required when the change of transmittance was 90% was counted as the response time.
The flexible electrochromic devices of examples 1 to 4 and comparative example 1 were subjected to voltage application, cycling was performed with the response time of color fading, and the cycling stability of the flexible electrochromic devices was evaluated, and the test results are shown in table 1, and the evaluation criteria are as follows:
v: the cycle times are more than or equal to 1000, and no bubbles are generated;
o: circulating for 500-800 times to generate bubbles;
x: the cycle times were < 50 times, and bubbles were generated.
Double eight five aging
The flexible electrochromic devices of examples 1 to 4 and comparative example 1 were placed at 85 ℃ and 85% RH, respectively, and after 100 hours of storage, the flexible electrochromic devices were discolored, response times were calculated, and cycling was performed with the discoloring response times, and the cycling stability of the flexible electrochromic devices was evaluated, and the test results are shown in table 1, and the evaluation criteria are as follows:
v: the cycle times are more than or equal to 1000, and no bubbles are generated;
o: circulating for 500-800 times to generate bubbles;
x: the cycle times were < 10 times, and bubbles were generated.
TABLE 1 Performance test
Figure BDA0003033962360000141
As can be seen from table 1, compared with comparative example 1, examples 1 to 4 have good cycling stability, shortened response time after aging, and excellent cycling stability, which illustrates that the addition of the buffer dielectric layer in examples 1 to 4 does not affect the color change performance of the original electrochromic device; on the other hand, in the electrolyte preparation and device assembly process or the device circulation and aging process, once water enters, the water participates in the conduction and color change process, the buffer medium layer can be used as an ion storage layer, the response time of the device is reduced, and the circulation performance is improved. The influence of water on the circulation stability of the device is greatly reduced, the circulation times of the device are obviously improved, the service life of the device is prolonged, and the device has a certain promotion effect on the promotion of industrialization.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (10)

1. A flexible electrochromic device, comprising: the flexible substrate of first flexible substrate, first conducting layer, electrochromic layer, quasi solid electrolyte layer, ion storage layer, second conducting layer and the flexible substrate of second that the stromatolite set up in proper order still including setting up the buffer dielectric layer of at least one side on quasi solid electrolyte layer.
2. The flexible electrochromic device according to claim 1, characterized in that it comprises: the plasma display panel comprises a first flexible substrate, a first conducting layer, an electrochromic layer, a first buffer medium layer, a quasi-solid electrolyte layer, a second buffer medium layer, an ion storage layer, a second conducting layer and a second flexible substrate which are sequentially stacked.
3. The flexible electrochromic device according to claim 1, wherein the material of the buffer medium layer is an inorganic compound;
optionally, the inorganic compound is selected from at least one of tantalum pentoxide, silicon oxide, chromium oxide, zirconium oxide, hafnium oxide, magnesium fluoride, calcium fluoride, and barium fluoride.
4. The flexible electrochromic device according to claim 1, wherein the thickness of the buffer medium layer is 50-200 nm.
5. The flexible electrochromic device according to claim 1, wherein said buffer medium layer is a loose porous structure film.
6. The flexible electrochromic device according to claim 1, wherein the buffer medium layer is prepared by a direct current magnetron reactive sputtering method or an electron beam method;
optionally, in the preparation process of the buffer medium layer, the coating speed is less than 0.5 nm/s;
optionally, the base film temperature is less than 50 ℃ during the preparation of the buffer medium layer.
7. The flexible electrochromic device according to claims 1 to 6, wherein the material of the quasi-solid electrolyte layer comprises a resin host, a plasticizer, a lithium salt, nano inorganic particles and an auxiliary agent;
optionally, the resin main body is selected from at least one of polyoxyethylene ether, polyvinylidene fluoride, polymethyl methacrylate and polyvinyl butyral;
optionally, the plasticizer is selected from at least one of ethylene carbonate, propylene carbonate, ethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether;
optionally, the lithium salt is selected from at least one of lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethanesulfonyl) imide, and lithium bis (pentafluoroethylsulfonyl) imide.
8. The flexible electrochromic device according to claims 1-6, wherein the material of the first flexible substrate and the material of the second flexible substrate are each independently selected from at least one of polyethylene terephthalate, polyethylene naphthalate, and polyimide;
optionally, the thickness of the first flexible substrate is 100-180 μm;
optionally, the thickness of the second flexible substrate is 100-180 μm;
optionally, the material of the first conductive layer and the material of the second conductive layer are each independently selected from at least one of tin-doped indium oxide, fluorine-doped tin oxide, and aluminum-doped zinc oxide.
9. The flexible electrochromic device according to claims 1-6, wherein the material of the electrochromic layer is selected from at least one of tungsten oxide, molybdenum oxide, niobium pentoxide and titanium dioxide;
optionally, the electrochromic layer has a thickness of 300-600 nm;
optionally, the material of the ion storage layer is selected from at least one of nickel oxide, iridium oxide, and manganese oxide;
optionally, the thickness of the ion storage layer is 200-450 nm.
10. A method of making the flexible electrochromic device of any one of claims 1-9, comprising:
sequentially preparing a first conductive layer, an electrochromic layer and a first buffer medium layer on the surface of a first flexible substrate so as to obtain a first composite layer; sequentially preparing a second conducting layer, an ion storage layer and a second buffer medium layer on the surface of a second flexible substrate so as to obtain a second composite layer; sequentially carrying out roll-to-roll hot-pressing compounding on the first composite layer, the quasi-solid electrolyte layer and the second composite layer so as to obtain a flexible electrochromic device;
or a first conductive layer, an electrochromic layer and a first buffer medium layer are sequentially prepared on the surface of the first flexible substrate so as to obtain a first composite layer; sequentially preparing a second conductive layer and an ion storage layer on the surface of a second flexible substrate so as to obtain a second composite layer; sequentially carrying out roll-to-roll hot-pressing compounding on the first composite layer, the quasi-solid electrolyte layer and the second composite layer so as to obtain a flexible electrochromic device;
or a first conductive layer and an electrochromic layer are sequentially prepared on the surface of the first flexible substrate so as to obtain a first composite layer; sequentially preparing a second conducting layer, an ion storage layer and a second buffer medium layer on the surface of a second flexible substrate so as to obtain a second composite layer; and sequentially carrying out roll-to-roll hot-pressing compounding on the first composite layer, the quasi-solid electrolyte layer and the second composite layer so as to obtain the flexible electrochromic device.
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