CN111487829B - Improved electrochromic device and mobile terminal comprising same - Google Patents
Improved electrochromic device and mobile terminal comprising same Download PDFInfo
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- CN111487829B CN111487829B CN202010444474.0A CN202010444474A CN111487829B CN 111487829 B CN111487829 B CN 111487829B CN 202010444474 A CN202010444474 A CN 202010444474A CN 111487829 B CN111487829 B CN 111487829B
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
-
- 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
-
- 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
Abstract
The invention relates to an improved electrochromic device which comprises a conductive substrate and an electrochromic material, wherein a porous MOFs membrane layer is deposited on the conductive substrate, and a cathode electrochromic material is grafted on the MOFs membrane layer. The improved electrochromic device has the advantages of high response speed, high contrast ratio and good cycling stability. The invention also discloses a mobile terminal comprising the improved electrochromic device, which meets the requirement of the appearance integrity of the mobile terminal and has huge market application prospect.
Description
Technical Field
The invention relates to the technical field of electrochromism, in particular to an improved electrochromism device and a mobile terminal comprising the same.
Background
Mobile terminals such as smart phones, IPADs and the like are generally provided with optical devices (camera modules, ambient light sensors, flash lamps and the like), and the optical devices need to be provided with light-transmitting areas at corresponding positions on the mobile terminals so as to receive and reflect light. The light-transmitting area on the existing mobile terminal does not have an electrochromic effect, but the appearance integrity of the mobile terminal is easily damaged due to the light-transmitting area, so that the visual attractiveness of the mobile terminal is reduced.
In order to improve the overall visual aesthetic degree of the mobile terminal, the electrochromic technology is applied to the mobile terminal and is more and more concerned by research personnel in the field; however, the conventional electrochromic device still has a low comprehensive performance level, and cannot meet the performance requirements of a mobile terminal and other special scenes on high response speed, high cycle stability and high contrast.
Disclosure of Invention
In view of the defects of the prior art, the invention provides an improved electrochromic device and a preparation method thereof on one hand, so as to solve the problems of low response speed, poor cycle stability, low contrast ratio and the like of the conventional electrochromic device, and make the electrochromic device more suitable for application in special scenes of mobile terminals such as mobile phones and the like.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
an improved electrochromic device comprises a conductive substrate and an electrochromic material, and is characterized in that a porous MOFs membrane layer is deposited on the conductive substrate, and a cathode electrochromic material is grafted on the MOFs membrane layer.
Preferably, the conductive substrate is composed of a substrate and a conductive material deposited on the substrate.
Preferably, the substrate is at least one of a substantially transparent polymer, glass, ceramic, and plastic. More preferably, the substrate is selected from substantially transparent glass.
Preferably, the conductive material is at least one of fluorine-doped tin oxide, aluminum-doped zinc oxide, indium tin oxide and indium zinc oxide. More preferably, the conductive material is fluorine-doped tin oxide.
Preferably, the MOFs membrane layer is a coordination polymer formed by self-assembling a multidentate organic ligand with a structural formula shown in a chemical formula I and transition metal ions.
Preferably, the transition metal ion is Zn 2+ 、Cu 2+ 、Ni 2+ 、Pd 2+ 、Pt 2+ 、Ru 2+ 、Co 2+ At least one of (1).
Preferably, the cathode electrochromic material is a compound with a structural formula shown as a chemical formula II,
in the formula: r1 is C1-C5 alkyl or benzyl, R2 is C1-C5 alkyl, and R3-R6 are independently selected from hydrogen, C1-C5 alkyl or C1-C5 alkoxy.
The invention provides a preparation method of an improved electrochromic device, which comprises the following steps:
s1, surface treatment: putting the conductive substrate cleaned by the deionized water into a mixed solvent consisting of ammonia water and hydrogen peroxide, and carrying out hydroxylation treatment on the surface of the conductive substrate;
s2, hydrothermal reaction: dissolving an organic ligand of a chemical formula I in a solvent, adding the solvent into a reaction tank, and reacting according to a molar ratio of the organic ligand to sodium hydroxide of 1:2, adding a sodium hydroxide solution, heating the reaction solution to 40-60 ℃, immersing the conductive substrate treated in the step S1 in the reaction solution, soaking for 5-30 min, adding a transition metal salt, adjusting the pH value to 3-7, raising the reaction temperature to 100-150 ℃, and continuing to react for 1-5 h to obtain the conductive substrate with the MOFs structural film layer; wherein the molar ratio of the organic ligand to the transition metal salt is 1:0.8 to 1.2;
s3, grafting a cathode electrochromic material: dissolving the cathode electrochromic material of the chemical formula II in tetrahydrofuran, then carrying out grafting reaction with the conductive substrate with the MOFs structural film layer obtained in the step S2, heating to 60-120 ℃, condensing and refluxing for 2-6 h to obtain a semi-finished product of the conductive substrate of the grafted cathode electrochromic material;
s4, manufacturing a finished product: and (4) bonding the semi-finished product of the conductive substrate obtained in the step (S3) with the substrate with the conductive reflecting film layer, defining a cavity, and pouring an anode electrochromic material and a solvent into the cavity to obtain the improved electrochromic device.
The invention also provides a mobile terminal, which comprises a camera and the electrochromic device, wherein the camera and the electrochromic device are arranged on the mobile terminal in a right-to-right way; when the mobile terminal does not start the camera shooting function, the electrochromic device is in a coloring state; and when the mobile terminal starts a camera shooting function, the electrochromic device is in a fading state.
Compared with the prior art, the invention has the beneficial effects that:
according to the improved electrochromic device, the deposition of the MOFs film layer structure and the grafting of the cathode electrochromic material are sequentially carried out on the conductive substrate, and the electrochromic response speed, the contrast and the circulation stability of the electrochromic device are improved through the modification treatment of the conductive substrate.
According to the improved electrochromic device, the triazine structure containing the carboxyl functional group is selected as the multidentate organic ligand, the conductive substrate and the cathode organic electrochromic material can be connected in a chemical bond combination mode, the comprehensive performance of the electrochromic device is improved, and due to the existence of the triazine functional group, the improved electrochromic device has the characteristic of ultraviolet radiation prevention and the aging resistance of the electrochromic device is improved.
The application discloses mobile terminal is provided with electrochromic device, through electrochromic device's quick response and high contrast, can hide the function that the inside camera of mobile terminal is not perceived when realizing that electrochromic device is painted, and can satisfy the effect of the inside camera normal function of making a video recording of mobile terminal when it fades, and then improve mobile terminal outward appearance wholeness.
Drawings
Fig. 1 is a front view of a mobile terminal according to an embodiment of the present invention;
fig. 2 is a rear view of a mobile terminal according to an embodiment of the present invention;
fig. 3 isbase:Sub>A cross-sectional view of the electrochromic device of fig. 2 taken along the directionbase:Sub>A-base:Sub>A.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments in the following description are given by way of example only, and other obvious variations will occur to those skilled in the art.
Example 1
The improved electrochromic device of the embodiment comprises the following steps:
s1, surface treatment: putting the conductive substrate cleaned by the deionized water into a mixed solvent consisting of ammonia water and hydrogen peroxide, and carrying out hydroxylation treatment on the surface of the conductive substrate; the volume ratio of the ammonia water to the hydrogen peroxide is 3:1;
s2, hydrothermal reaction: dissolving an organic ligand of a chemical formula I in a DMF solvent, adding the solution into a reaction tank, and then mixing the solution according to the molar ratio of the organic ligand to sodium hydroxide of 1:2, adding a sodium hydroxide solution, heating the reaction solution to 50 ℃, immersing the conductive substrate treated in the step 1 in the reaction solution, soaking for 15min, adding a zinc nitrate solution with the mass concentration of 20wt%, adjusting the pH value to 6, raising the reaction temperature to 120 ℃, and continuing to react for 3h to obtain the conductive substrate with the MOFs structural film layer; wherein the molar ratio of the organic ligand to the zinc nitrate is 1:1; the mass ratio of the organic ligand to the DMF solvent is 20:100, respectively;
s3, grafting a cathode electrochromic material: dissolving the cathode electrochromic material of the chemical formula II-a in tetrahydrofuran, then carrying out a grafting reaction with the conductive substrate with the MOFs structural film layer obtained in the step S2, heating at 90 ℃, condensing and refluxing for 4 hours to obtain a semi-finished product of the conductive substrate of the grafted cathode electrochromic material; the mass ratio of the cathode electrochromic material to tetrahydrofuran is 30:100, respectively;
s4, manufacturing a finished product: and (4) attaching the semi-finished product of the conductive substrate obtained in the step (S3) to a substrate with a conductive reflecting film layer, defining a cavity, filling 0.5g of 5, 10-diisopropyl-5,10-dimethylphenazine and 20mL of propylene carbonate solvent into the cavity, and sealing the opening by using UV (ultraviolet) glue to obtain the improved electrochromic device.
The synthetic route of the chemical formula II-a is as follows:
s1: dissolving 0.02mol of 4,4' -bipyridine in 20mL of acetonitrile solution, adding 0.02mol of 2-bromoethanol for chemical reaction, controlling the heating, condensing and refluxing reaction temperature to be 80 ℃ and the reaction time to be 12 hours to obtain a mixed solution of bipyridine salt intermediate products;
s2: adding 0.02mol of bromoethane into the mixed solution obtained in the step S1, continuously carrying out chemical reaction at the reaction temperature of 80 ℃, and carrying out heating, condensing and refluxing reaction for 8 hours;
s3: and after the reaction is finished, filtering the obtained mixed solution, dissolving a filter cake in deionized water, adding sodium fluoborate to generate a large amount of precipitate, and filtering the precipitate to obtain the target product of the chemical formula II-a.
Example 2
The improved electrochromic device of the embodiment comprises the following steps:
s1, surface treatment: putting the conductive substrate cleaned by the deionized water into a mixed solvent consisting of ammonia water and hydrogen peroxide, and carrying out hydroxylation treatment on the surface of the conductive substrate; the volume ratio of the ammonia water to the hydrogen peroxide is 1:1;
s2, hydrothermal reaction: dissolving an organic ligand of a chemical formula I in a DMF solvent, adding the solution into a reaction tank, and then mixing the solution according to the molar ratio of the organic ligand to sodium hydroxide of 1:2, adding a sodium hydroxide solution, heating the reaction solution to 40 ℃, immersing the conductive substrate treated in the step 1 in the reaction solution, soaking for 30min, adding a zinc nitrate solution with the mass concentration of 20wt%, adjusting the pH value to 4, raising the reaction temperature to 100 ℃, and continuing to react for 5h to obtain the conductive substrate with the MOFs structural film layer; wherein the molar ratio of the organic ligand to the zinc nitrate is 1:0.8; the mass ratio of the organic ligand to the DMF solvent is 25:100, respectively;
s3, grafting a cathode electrochromic material: dissolving the cathode electrochromic material of the chemical formula II-b in tetrahydrofuran, then carrying out a grafting reaction with the conductive substrate with the MOFs structural film layer obtained in the step S2, heating at 80 ℃, condensing and refluxing for 3 hours to obtain a semi-finished product of the conductive substrate of the grafted cathode electrochromic material; the mass ratio of the cathode electrochromic material to tetrahydrofuran is 30:100, respectively;
s4, manufacturing a finished product: and (4) bonding the semi-finished product of the conductive substrate obtained in the step (S3) with the substrate with the conductive reflecting film layer, defining a cavity, pouring 0.5g of 5, 10-diisopropyl-5,10-dimethylphenazine and 20mL of propylene carbonate solvent into the cavity, and sealing by using UV (ultraviolet) glue to obtain the improved electrochromic device.
The synthetic route of the chemical formula II-b is as follows:
s1: dissolving 0.02mol of 4,4' -bipyridine in 20mL of acetonitrile solution, adding 0.02mol of 3-bromo-1-propanol for chemical reaction, controlling the heating, condensing and refluxing reaction temperature to be 80 ℃ and the reaction time to be 12 hours to obtain a mixed solution of bipyridine salt intermediate products;
s2: adding 0.02mol of 1-bromopropane into the mixed solution obtained in the step S1, continuously carrying out chemical reaction at the reaction temperature of 80 ℃, and carrying out heating, condensing and refluxing reaction for 8 hours;
s3: and after the reaction is finished, filtering the obtained mixed solution, dissolving a filter cake in deionized water, adding sodium fluoborate to generate a large amount of precipitate, and filtering the precipitate to obtain the target product of the chemical formula II-b.
Example 3
The improved electrochromic device of the embodiment comprises the following steps:
s1, surface treatment: putting the conductive substrate cleaned by the deionized water into a mixed solvent consisting of ammonia water and hydrogen peroxide, and carrying out hydroxylation treatment on the surface of the conductive substrate; the volume ratio of the ammonia water to the hydrogen peroxide is 2:1;
s2, hydrothermal reaction: dissolving an organic ligand of a chemical formula I in a DMF solvent, adding the solution into a reaction tank, and adding the solution into a reaction tank according to a molar ratio of the organic ligand to sodium hydroxide of 1:2, adding a sodium hydroxide solution, heating the reaction solution to 60 ℃, immersing the conductive substrate treated in the step 1 in the reaction solution, soaking for 5min, adding a zinc nitrate solution with the mass concentration of 20wt%, adjusting the pH value to 5, raising the reaction temperature to 150 ℃, and continuing to react for 1h to obtain the conductive substrate with the MOFs structural film layer; wherein the molar ratio of the organic ligand to the zinc nitrate is 1:1.2; the mass ratio of the organic ligand to the DMF solvent is 30:100, respectively;
s3, grafting a cathode electrochromic material: dissolving the cathode electrochromic material of the chemical formula II-c in tetrahydrofuran, then carrying out a grafting reaction with the conductive substrate with the MOFs structural film layer obtained in the step S2, heating at 120 ℃, condensing, refluxing and reacting for 2 hours to obtain a semi-finished product of the conductive substrate grafted with the cathode electrochromic material; the mass ratio of the cathode electrochromic material to tetrahydrofuran is 20:100, respectively;
s4, manufacturing a finished product: and (4) attaching the semi-finished product of the conductive substrate obtained in the step (S3) to a substrate with a conductive reflecting film layer, defining a cavity, filling 0.5g of 5, 10-diisopropyl-5,10-dimethylphenazine and 20mL of propylene carbonate solvent into the cavity, and sealing the opening by using UV (ultraviolet) glue to obtain the improved electrochromic device.
The synthetic route of the chemical formula II-c is as follows:
s1: dissolving 0.02mol of 4,4' -bipyridine in 20mL of acetonitrile solution, adding 0.02mol of 4-bromo-1-butanol, performing chemical reaction, controlling the heating, condensing and refluxing reaction temperature to be 80 ℃, and reacting for 12 hours to obtain a mixed solution of bipyridine salt intermediate products;
s2: adding 0.02mol of bromobutane into the mixed solution obtained in the step S1, continuously carrying out chemical reaction at the reaction temperature of 80 ℃, and carrying out heating, condensing and refluxing reaction for 8 hours;
s3: and after the reaction is finished, filtering the obtained mixed solution, dissolving a filter cake in deionized water, adding sodium fluoborate to generate a large amount of precipitate, and filtering the precipitate to obtain the target product of the chemical formula II-c.
Application example
Referring to fig. 1 to 2, in an application example, the mobile terminal 100 is a smart phone. In other embodiments, the mobile terminal 100 may be a tablet, a palmtop, or the like. The mobile terminal 100 comprises a shell assembly, an optical device 3, a circuit board, a battery and the like, wherein the shell assembly comprises a shell and an electrochromic device 21 arranged on the shell, the optical device 3, the circuit board and the battery are arranged in the shell assembly, the battery is connected to the circuit board and can supply power to the circuit board and the optical device 3, and the circuit board can be used for adjusting the voltage of the electrochromic device 21. The housing comprises a front housing 1 provided with a display screen module 11 and a rear housing 2 departing from the display screen module 11, an inner cavity capable of bearing and accommodating components such as an optical device 3, a circuit board and a battery is defined between the front housing 1 and the rear housing 2, and the rear housing 2 is sometimes called as a rear cover, a rear housing or a battery cover. The rear case 2 may be made of a metal material such as aluminum alloy, magnesium alloy, stainless steel, etc., and the rear case 2 may be made of a non-metal material such as glass, ceramic, plastic, resin, etc. The rear shell 2 is provided with a through hole so that light can be incident on the optical device 3, and the size of the through hole is matched with the arrangement area range of the optical device. The electrochromic device 21 is fixedly connected to the through hole of the rear housing 2, so that the electrochromic device 21 and the optical device 3 are arranged at corresponding positions.
The optical device 3 may include one or more of a camera module, a flash, and a focus sensor. The camera module can be used for collecting images, such as photographing, video recording, video call and the like. The flash lamp can be used to the rear camera light filling to promote the shooting quality of rear camera. The focusing sensor can be used for focusing the camera module in the shooting process so as to improve the shooting quality of the camera module.
Referring to fig. 3, the electrochromic device 21 includes: a first substantially transparent conductive substrate; a second substantially transparent conductive substrate, said first and second conductive substrates being disposed in spaced apart relation; a sealing member disposed substantially circumferentially between peripheral regions of the first and second electrically conductive substrates to sealingly bond oppositely disposed surfaces of the first and second electrically conductive substrates to each other and define a cavity; the cavity is filled with an anode electrochromic material and a solvent. The first conductive substrate is a glass substrate 211 plated with a transparent conductive film 214, the second conductive substrate is a glass substrate 212 plated with a conductive reflective layer 215, the transparent conductive film 214 and the conductive reflective layer 215 are respectively electrically connected with corresponding electrodes, a sealed cavity 216 is formed on the glass substrate between the transparent conductive film 214 and the conductive reflective layer 215 by bonding a sealing member epoxy resin 213, and an electrochromic material 217 is poured into the sealed cavity 216. The transparent conductive film 214 is a conductive material modified in embodiments 1 to 3, and the resistance of the transparent conductive film 214 is preferably less than 25 ohms. The conductive reflective layer 215 is a chromium, silver, aluminum, stainless steel or nickel layer, or an alloy layer composed of two or more of the above metal elements.
The optical device 3 and the electrochromic device 21 are arranged on the mobile terminal 100 in a facing manner, that is, the electrochromic device 21 covers the optical device 3; when the mobile terminal 100 does not start the camera function, the electrochromic device 21 is in a coloring state, at this time, the light transmittance of the electrochromic device 21 is low, and the optical device 3 is shielded by the electrochromic device 21 and is not easy to be perceived, so that the overall appearance integrity of the mobile terminal is improved; furthermore, the color of the electrochromic device 21 after being changed is matched with the appearance color of the rear shell, so that the visual attractiveness of the mobile terminal is further improved; when the mobile terminal 100 starts the camera function, the electrochromic device 21 responds quickly to make it in a fading state, and at this time, the light transmittance of the electrochromic device 21 is high, and the normal functional use of the optical device 3 is not affected.
Application example 1
The electrochromic device prepared in example 1 is fixedly connected to the rear case provided with the through hole, and the rear case is covered on the front case accommodating the optical device, the circuit board, the battery and other parts to assemble a complete smart phone, wherein the electrochromic device is arranged opposite to the optical device.
Conventional performance tests were conducted on electrochromic devices, wherein the aging resistance tests were conducted in an aging resistant box, with ultraviolet lamp aging (280-400 nm), with the results shown in table 1:
TABLE 1
| Test items | Performance index |
| Transmittance in transparent state | 82.7％ |
| Transmittance in colored state | 9.5％ |
| Contrast ratio | 73 |
| Color change response time | 0.75s |
| Fade response time | 0.76s |
| Aging resistance time | >168h |
| Circulation stability (number of fades) | >10000 |
Application example 2
The electrochromic device prepared in example 2 is fixedly connected to the rear case provided with the through hole, and the rear case is covered on the front case accommodating the optical device, the circuit board, the battery and other parts to assemble a complete smart phone, wherein the electrochromic device is arranged right opposite to the optical device.
Conventional performance tests were conducted on electrochromic devices, where the aging resistance test was conducted in an aging resistant cabinet, ultraviolet lamp aging (280-400 nm), and the results are shown in table 2:
TABLE 2
Application example 3
The electrochromic device prepared in example 3 was fixedly connected to the rear case with the through-hole, and the rear case was covered on the front case containing the optical device, the circuit board, the battery, and other parts to assemble a complete smart phone, with the electrochromic device facing the optical device.
Conventional performance tests were conducted on electrochromic devices, wherein the aging resistance tests were conducted in an aging resistant box, with ultraviolet lamp aging (280-400 nm), with the results shown in table 3:
TABLE 3
| Test items | Performance index |
| Transmittance in transparent state | 82.5％ |
| Transmittance in colored state | 8.6％ |
| Contrast ratio | 74 |
| Color change response time | 0.72s |
| Fade response time | 0.74s |
| Aging resistance time | >168h |
| Circulation stability (number of fades) | >10000 |
It can be seen that the present invention has considerable advantages over the currently used technology. The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which fall within the scope of the invention as claimed.
Claims (7)
1. An improved electrochromic device comprises a conductive substrate and an electrochromic material, and is characterized in that a porous MOFs membrane layer is deposited on the conductive substrate, and a cathode electrochromic material is grafted on the MOFs membrane layer; the MOFs membrane layer is a coordination polymer formed by self-assembling a multidentate organic ligand with a structural formula shown as a chemical formula I and transition metal ions,
the cathode electrochromic material is a compound with a structural formula shown in a chemical formula II,
in the formula: r is 1 Is C1-C5 alkyl or benzyl, R 2 Is C1-C5 alkyl, R 3 -R 6 Each independently selected from hydrogen, C1-C5 alkyl or C1-C5 alkoxy.
2. An improved electrochromic device as in claim 1, wherein said electrically conductive substrate is comprised of a substrate and an electrically conductive material deposited on said substrate.
3. An improved electrochromic device as in claim 2, wherein said substrate is selected from at least one of a substantially transparent polymer, glass, ceramic, and plastic.
4. An improved electrochromic device as in claim 2, wherein said conductive material is selected from at least one of fluorine doped tin oxide, aluminum doped zinc oxide, indium tin oxide, indium zinc oxide.
5. An improved electrochromic device as claimed in claim 1, characterized in that said transition metal ion is Zn 2+ 、Cu 2+ 、Ni 2+ 、Pd 2+ 、Pt 2+ 、Ru 2+ 、Co 2+ At least one of (1).
6. A method of making an improved electrochromic device according to claim 1, characterized in that it comprises the following steps:
s1, surface treatment: putting the conductive substrate cleaned by the deionized water into a mixed solvent consisting of ammonia water and hydrogen peroxide, and carrying out hydroxylation treatment on the surface of the conductive substrate;
s2, hydrothermal reaction: dissolving an organic ligand of a chemical formula I in a solvent, adding the solvent into a reaction tank, and adding the organic ligand and sodium hydroxide according to a molar ratio of 1:2, adding a sodium hydroxide solution, heating the reaction solution to 40-60 ℃, immersing the conductive substrate treated in the step S1 in the reaction solution, soaking for 5-30 min, adding a transition metal salt, adjusting the pH value to 3-7, raising the reaction temperature to 100-150 ℃, and continuing to react for 1-5 h to obtain the conductive substrate with the MOFs structural film layer; wherein the molar ratio of the organic ligand to the transition metal salt is 1:0.8 to 1.2;
s3, grafting a cathode electrochromic material: dissolving the cathode electrochromic material of the chemical formula II in tetrahydrofuran, then carrying out grafting reaction on the cathode electrochromic material and the conductive substrate with the MOFs structural film layer obtained in the step S2, heating to 60-120 ℃, condensing, refluxing and reacting for 2-6 hours to obtain a semi-finished product of the conductive substrate of the grafted cathode electrochromic material;
s4, manufacturing a finished product: and (4) bonding the semi-finished product of the conductive substrate obtained in the step (S3) with the substrate with the conductive reflecting film layer, defining a cavity, and pouring an anode electrochromic material and a solvent into the cavity to obtain the improved electrochromic device.
7. A mobile terminal, characterized in that the mobile terminal comprises a camera and an electrochromic device as claimed in any one of claims 1 to 6, wherein the camera and the electrochromic device are arranged on the mobile terminal; when the mobile terminal does not start the camera shooting function, the electrochromic device is in a coloring state; and when the mobile terminal starts a camera shooting function, the electrochromic device is in a fading state.
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| CN101921262B (en) * | 2010-08-18 | 2013-07-31 | 宁波祢若电子科技有限公司 | Compound used as electrochromic material as well as preparation method and application thereof |
| CN104324756B (en) * | 2014-10-09 | 2016-06-22 | 济南大学 | A kind of preparation method and application of mesoporous metal organic coordination compound based composites |
| CN106916099A (en) * | 2015-12-25 | 2017-07-04 | 宁波祢若电子科技有限公司 | A kind of cathodic electrochromic compound in electrochromic device and preparation method thereof |
| CN106916317B (en) * | 2017-02-27 | 2019-10-08 | 三峡大学 | A kind of Rare Earth Europium base organic crystalline material, preparation and the application on fluorescence identifying antibiotic |
| CN108051970B (en) * | 2017-12-21 | 2020-06-19 | 东华大学 | Preparation method of MOFs-based colorful electrochromic intelligent display device |
| CN209962060U (en) * | 2019-05-30 | 2020-01-17 | Oppo广东移动通信有限公司 | Electronic equipment, shell assembly and electrochromic device thereof |
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