CN113759625A - High-concentration aqueous zinc ion electrolyte, electrochromic device containing electrolyte and electrochromic method - Google Patents
High-concentration aqueous zinc ion electrolyte, electrochromic device containing electrolyte and electrochromic method Download PDFInfo
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 52
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 23
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 76
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 38
- 239000011592 zinc chloride Substances 0.000 claims abstract description 38
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 34
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000000758 substrate Substances 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 17
- 229920002379 silicone rubber Polymers 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 238000003980 solgel method Methods 0.000 claims description 7
- 238000004528 spin coating Methods 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 238000009831 deintercalation Methods 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- 238000004544 sputter deposition Methods 0.000 claims description 4
- 238000005285 chemical preparation method Methods 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 5
- 239000010409 thin film Substances 0.000 claims 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001930 tungsten oxide Inorganic materials 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000004040 coloring Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000003446 memory effect Effects 0.000 abstract description 3
- 238000009830 intercalation Methods 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 238000007614 solvation Methods 0.000 abstract description 2
- 230000004044 response Effects 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000004984 smart glass Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 230000001680 brushing effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000005289 physical deposition Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
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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
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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Abstract
The invention discloses a high-concentration water-based zinc ion electrolyte, an electrochromic device containing the electrolyte and a method, wherein the mass molar concentration of a zinc chloride aqueous solution is controlled to be 8-31 mol/kg. Under the electrolyte system, the electrolyte salt and water molecules are subjected to solvation, so that the activity of free water molecules is reduced, the electrochemical window is widened to 2.4V, the decoloring voltage of an electrochromic device can be improved, and the electron de-intercalation rate of electrochromic reaction is further improved; the side reaction of free water is inhibited, and the electrochemical stability of the device is improved; the high concentration and high quality ensure excellent open-circuit memory effect. Therefore, the electrochromic device taking a transparent metal oxide film such as tungsten oxide and the like as an electrochromic layer, a metal zinc foil as a counter electrode and a high-concentration water-based zinc chloride solution as an electrolyte has excellent comprehensive performance, has higher coloring/decoloring response speed, and has good cycle stability and open-circuit memory effect.
Description
Technical Field
The invention belongs to the technical field of electrochromism, and particularly relates to a high-concentration water system zinc ion electrolyte, an electrochromism device containing the electrolyte and a method.
Background
Electrochromism refers to reversible change of optical properties (absorption rate, transmittance or reflectivity) of an electrochromic material under the driving of an external electric field. Electrochromic devices based on aqueous zinc ion electrolytes have attracted considerable attention due to their advantages of low cost, safety, and wide variety. However, the electrochemical activity of the aqueous zinc ion electrolyte is limited by the narrow electrochemical window (1.23V) of water, and the side reaction of zinc ions and free water molecules can affect the deintercalation of zinc ions in the electrochromic material, further affect the electrochemical stability of the electrochromic device, and further affect the electrochromic performance. Therefore, optimization of aqueous zinc ion electrolytes plays a crucial role in electrochemical stability and electrochromic performance of devices.
Disclosure of Invention
In order to overcome the above technical problems, an object of the present invention is to provide a high-concentration aqueous zinc ion electrolyte, and an electrochromic device and method including the same, in which an electrolyte salt reacts with water molecules by solvation, so as to reduce the activity of free water molecules, widen an electrochemical window to 2.4V, suppress side reactions of free water, and improve the electrochemical stability of the device, thereby obtaining an electrochromic device having excellent performance: the electrochromic device which takes the metal oxide film as the electrochromic layer material, the metal zinc foil as the counter electrode and the high-concentration water-based zinc ion solution as the electrolyte has the electrochromic characteristic of excellent comprehensive performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
the high-concentration water-based zinc ion electrolyte is a zinc chloride solution, and the mass molar concentration of the electrolyte is controlled to be 8-31 mol/kg.
The electrochromic device comprises a transparent conductive substrate, a metal oxide film, a zinc foil and a zinc chloride aqueous solution.
The preparation method of the electrochromic device comprises the following steps;
1) preparation of metal oxide film:
selecting appropriate metal oxide related raw materials, and obtaining a transparent metal oxide film by adopting a common physical-chemical preparation method (a sol-gel method, an electrochemical deposition method, a hydrothermal method and the like);
2) preparation of aqueous zinc ion electrolyte:
dissolving zinc chloride powder with different masses in water, and stirring and dissolving to obtain zinc chloride aqueous solutions with different mass molar concentrations;
3) preparing an electrochromic device:
and (2) encapsulating the zinc chloride aqueous solution and the zinc foil obtained in the step 2) and the metal oxide film on the transparent conductive substrate obtained in the step 1) by using silicon rubber to obtain the electrochromic device.
The specific operation of the step 1):
the electrochromic material is an inorganic metal oxide capable of carrying out reversible deintercalation of zinc ions, and generates a corresponding electrochromic phenomenon. Specifically, the preparation process comprises the steps of preparing a precursor containing metal elements such as tungsten and molybdenum by a chemical solution method, preparing a film by processes such as spin coating and blade coating, and annealing to obtain the metal oxide, or directly evaporating and sputtering a metal oxide layer on a transparent conductive substrate.
The specific operation of the step 2) is as follows:
10.904g to 42.253g of zinc chloride powder is added into 10ml of deionized water, and the mass molar concentration of the obtained zinc ion electrolyte solution is 8mol/kg to 31 mol/kg.
The specific operation of the step 3) is as follows:
assembling the metal oxide film on the transparent conductive substrate with silicon rubber and the transparent substrate adhered with the zinc foil, and encapsulating the aqueous zinc chloride electrolyte to obtain the electrochromic device.
The invention has the beneficial effects that:
the invention firstly proposes that the high-concentration aqueous (water-in-salt) electrolyte is applied to the field of electrochromism, and under the electrolyte system, the electrochemical window is widened to 2.4V, the decoloring voltage of electrochromism is improved, and the electron de-intercalation rate of electrochromism reaction is further improved; the side reaction of free water molecules is inhibited, and the electrochemical stability is improved; the high concentration profile ensures excellent color memory effects. Meanwhile, the electrolyte has good conductivity, is green and safe, and the electrochromic device containing the electrolyte is simple to prepare, thereby having considerable application prospect in the fields of building energy-saving windows, intelligent display devices and the like.
Drawings
Fig. 1 is a schematic diagram of the electrochemical window of a high concentration aqueous zinc ion electrolyte.
Fig. 2 is a schematic structural diagram of an electrochromic smart window device according to the first embodiment.
Fig. 3 is a schematic structural diagram of an electrochromic display device according to the first embodiment.
Fig. 4 is a schematic view of the cycling stability of the electrochromic smart window device of the first embodiment.
Fig. 5 is a graph showing a transmittance spectrum with respect to a standing time in an open state of the electrochromic display device according to the first embodiment.
Fig. 6 is an optical photograph of the electrochromic display device according to the first embodiment in an open state, as a function of the standing time.
Detailed Description
The present invention will be described in further detail with reference to examples.
The mass molar concentration of the high-concentration aqueous zinc ion electrolyte is controlled to be 8-31 mol/kg, the good transmittance can be kept in the concentration range, and the electrochemical window is stabilized at 2.4V (figure 1), so that the decolorizing voltage of an electrochromic device based on the electrolyte is set to be 2V.
The invention discloses a high-concentration water-based zinc ion electrolyte, which is a zinc chloride aqueous solution, and the mass molar concentration of the electrolyte is controlled to be 8-31 mol/kg. The electrochromic device comprises a transparent metal oxide film, a zinc foil and a zinc chloride aqueous solution. The method comprises the following specific steps:
1) preparation of metal oxide film: selecting appropriate metal oxide related raw materials, and obtaining a transparent metal oxide film by adopting a common physical and chemical preparation method (a sol-gel method, an electrochemical deposition method, a hydrothermal method, a sputtering method and the like);
2) preparation of aqueous zinc ion electrolyte: dissolving zinc chloride powder with different masses in an aqueous solution, stirring and dissolving at room temperature to obtain zinc chloride aqueous solutions with different mass molar concentrations;
3) preparing an electrochromic device: and (2) encapsulating the zinc foil and the transparent metal oxide film obtained in the step 1) with silicon rubber by using a zinc chloride aqueous solution to obtain the electrochromic device.
The specific operation of the step 1) is as follows:
the selected electrochromic material is an inorganic metal oxide capable of carrying out reversible deintercalation of zinc ions, and generates a corresponding electrochromic phenomenon. Specifically, metal oxides including tungsten oxide, molybdenum oxide, titanium oxide, and the like, and composite materials thereof may be included. The preparation process can be a chemical solution method, a precursor containing metal elements such as tungsten, molybdenum and the like is prepared, a film is prepared through processes such as spin coating, scraper coating and the like, and the metal oxide is obtained through annealing. Or directly evaporating and sputtering the metal oxide layer on the transparent conductive substrate by using a physical deposition method.
The specific operation of the step 2) is as follows: 10.904g to 42.253g of zinc chloride powder is added into 10ml of deionized water, stirred and dissolved at room temperature, and the mass molar concentration of the obtained zinc chloride electrolyte is 8mol/kg to 31 mol/kg.
The specific operation of the step 3) is as follows:
and assembling the metal oxide film uniformly deposited on the transparent conductive substrate with the silicon rubber and the transparent substrate adhered with the zinc foil, and packaging the aqueous zinc chloride electrolyte to obtain the electrochromic device.
Example one
The high-concentration zinc ion electrolyte and the electrochromic device comprising the same comprise the following steps:
1) preparation of metal oxide film: taking tungstic acid as a reaction raw material, spin-coating or brush-coating a tungsten oxide precursor sol on a transparent conductive substrate by adopting a sol-gel method, and carrying out carbonization-annealing treatment to obtain a transparent tungsten oxide film;
2) preparation of aqueous zinc ion electrolyte: adding 27.26g of zinc chloride powder into 10ml of water, stirring and dissolving at room temperature to form a high-concentration water-based zinc chloride electrolyte, wherein the mass molar concentration of the electrolyte is 20 mol/kg;
3) preparing an electrochromic device: and (2) encapsulating the zinc foil and the transparent tungsten oxide film obtained in the step 1) with silicon rubber by using a zinc chloride aqueous solution to obtain the electrochromic device.
The specific operation of the step 1) is as follows:
mixing 4g of tungstic acid serving as a reaction raw material with 50ml of hydrogen peroxide, 50ml of deionized water and polyvinylpyrrolidone (PVP) with the mass fraction of the solution being 5%, stirring, dissolving and concentrating for 4h in an oil bath kettle environment at the temperature of 90 ℃, and obtaining the corresponding precursor sol.
The precursor sol is prepared by spin coating (1500r/min,10s,3 times) or brush coating on a transparent conductive substrate by a sol-gel method. The corresponding uniformly coated or patterned transparent tungsten oxide film is obtained by a carbonization (350 ℃) -annealing (500 ℃, 2h) process.
The specific operation of the step 3) is as follows:
the tungsten oxide films uniformly spin-coated on the two transparent conductive substrates are respectively placed in a face-to-face mode through silicon rubber adhesion, a water-based zinc chloride electrolyte is packaged, and a zinc foil is embedded between the two layers of silicon rubber to obtain the electrochromic intelligent window device (the device structure is shown in figure 2);
and (3) packaging the zinc chloride aqueous solution and the patterned transparent tungsten oxide film prepared by brushing in the step 1) through the transparent substrate adhered with the zinc foil to obtain the electrochromic display device (the device structure is shown in figure 3).
Example two
The high-concentration zinc ion electrolyte and the electrochromic device comprising the same comprise the following steps:
1) preparation of metal oxide film: tungsten powder is used as a reaction raw material to react with hydrogen peroxide (H)2O2) After ice-bath reaction, taking supernatant obtained by ultrasonic filtration as precursor sol, carrying out spin coating preparation on a transparent conductive substrate by a sol-gel method and carrying out subsequent annealing process to obtain a transparent tungsten oxide film;
2) preparation of aqueous zinc ion electrolyte: 10.904g of zinc chloride powder is added into 10ml of deionized water, and stirred and dissolved at room temperature to form a high-concentration water-based zinc chloride electrolyte, wherein the mass molar concentration of the electrolyte is 8 mol/kg.
3) Preparing an electrochromic device: and (2) encapsulating the zinc foil and the transparent metal oxide film obtained in the step 1) with silicon rubber by using a zinc chloride aqueous solution to obtain the electrochromic device.
The specific operation of the step 1) is as follows:
reacting 10g of tungsten powder with 50ml of hydrogen peroxide solution in an ice-water bath, drying the reacted supernatant at 70 ℃ to obtain a tungsten complex, ultrasonically dispersing the tungsten complex in ethanol for 1h, standing and filtering to obtain tungsten oxide precursor sol, spin-coating (1000r/min,8s and 4 times) the precursor sol on a transparent conductive substrate by a sol-gel method, and annealing at 400 ℃ for 30min to obtain the transparent tungsten oxide film.
The specific operation of the step 3) is as follows:
and (2) closely packaging the transparent substrate adhered with the zinc foil and the transparent tungsten oxide film prepared by brushing in the step 1) by using annular silicon rubber, and assembling zinc chloride aqueous solution to obtain the electrochromic device.
EXAMPLE III
The high-concentration zinc ion electrolyte and the electrochromic device comprising the same comprise the following steps:
1) preparation of metal oxide film: molybdenum powder is used as a reaction raw material, and is reacted with hydrogen peroxide cold water in a water bath to obtain orange red transparent sol, the orange red transparent sol is subjected to reduced pressure distillation, absolute ethyl alcohol is added to be used as a solvent, a flat and uniform film is prepared on the surface of a transparent substrate through a dipping-pulling method, and the transparent molybdenum oxide film is obtained through further annealing treatment.
2) Preparation of aqueous zinc ion electrolyte: 13.63g of zinc chloride powder is added into 10ml of deionized water, and stirred and dissolved at room temperature to form a high-concentration water-based zinc chloride electrolyte, wherein the mass molar concentration of the electrolyte is 10 mol/kg.
3) Preparing an electrochromic device: and (2) encapsulating the zinc foil and the transparent molybdenum oxide film obtained in the step 1) with a zinc chloride aqueous solution to obtain the electrochromic device.
The specific operation of the step 1) is as follows:
taking 5g of molybdenum powder as a reaction raw material, stirring and reacting with 35ml of hydrogen peroxide solution in a cold water bath, standing, centrifuging, taking supernate to obtain orange red sol, carrying out reduced pressure distillation at 45 ℃, adding absolute ethyl alcohol to obtain molybdenum oxide precursor sol, vertically lifting a transparent substrate at the speed of 5cm/min by using a dipping-lifting method, and heating at the constant temperature of 50 ℃ for 30min to obtain the transparent molybdenum oxide film.
The specific operation of the step 3) is as follows:
and (2) closely packaging the transparent substrate adhered with the zinc foil and the transparent molybdenum oxide film prepared by brushing in the step 1) by using annular silicon rubber, and assembling zinc chloride aqueous solution to obtain the electrochromic device.
According to the manufacturing process of example 1, as shown in fig. 4, the electrochromic smart window device based on 20mol/kg aqueous zinc chloride electrolyte shows no tendency of attenuation of transmittance and light modulation range in the colored state and the decolored state under the conditions that coloring voltage is 0V for 6s and decoloring voltage is 2V for 15s and 300 cycles are performed, and thus, the electrochromic smart window device shows excellent cycle stability. Fig. 5 is a spectrogram of transmittance changing with time in an open state when the electrochromic display device of the first embodiment displays "west ampere big" by self-coloring, and the light modulation ranges (@660nm) in the initial state, the state of being left for 1 day, the state of being left for 2 days, and the state of being left for 3 days are constantly smaller, which are 71.38%, 54.85%, 42.68%, and 28.1%, respectively. The corresponding optical photographs in each state are shown in fig. 6.
Claims (6)
1. The high-concentration water-based zinc ion electrolyte is characterized in that the electrolyte is a zinc chloride solution, and the mass molar concentration of the electrolyte is controlled to be 8-31 mol/kg.
2. An electrochromic device, characterized by comprising a transparent conductive substrate, a metal oxide thin film, a zinc foil and an aqueous solution of zinc chloride.
3. The method for preparing an electrochromic device according to claim 2, comprising the steps of;
1) preparation of metal oxide film:
selecting appropriate metal oxide related raw materials, and obtaining a transparent metal oxide film by adopting a common physical-chemical preparation method (a sol-gel method, an electrochemical deposition method, a hydrothermal method and the like);
2) preparation of aqueous zinc ion electrolyte:
dissolving zinc chloride powder with different masses in water, and stirring and dissolving to obtain zinc chloride aqueous solutions with different mass molar concentrations;
3) preparing an electrochromic device:
and (2) encapsulating the zinc chloride aqueous solution and the zinc foil obtained in the step 2) and the metal oxide film on the transparent conductive substrate obtained in the step 1) by using silicon rubber to obtain the electrochromic device.
4. The method for preparing an electrochromic device according to claim 3, characterized in that the specific operations of step 1):
the electrochromic material is an inorganic metal oxide capable of carrying out reversible deintercalation of zinc ions, and generates a corresponding electrochromic phenomenon. Specifically, the preparation process comprises the steps of preparing a precursor containing metal elements such as tungsten and molybdenum by a chemical solution method, preparing a film by processes such as spin coating and blade coating, and annealing to obtain the metal oxide, or directly evaporating and sputtering a metal oxide layer on a transparent conductive substrate.
5. The method for preparing an electrochromic device according to claim 3, wherein the specific operation of step 2) is:
10.904g to 42.253g of zinc chloride powder is added into 10ml of deionized water, and the mass molar concentration of the obtained zinc ion electrolyte solution is 8mol/kg to 31 mol/kg.
6. The method for preparing an electrochromic device according to claim 3, wherein the specific operation of step 3) is:
and assembling the metal oxide film uniformly deposited on the transparent conductive substrate with the silicon rubber and the transparent substrate adhered with the zinc foil, and packaging the aqueous zinc chloride electrolyte to obtain the electrochromic device.
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| CN114839818A (en) * | 2022-04-13 | 2022-08-02 | 西安交通大学 | Iron ion electrolyte tungsten oxide-based multicolor electrochromic device and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3905834A (en) * | 1968-08-08 | 1975-09-16 | Matsushita Electric Ind Co Ltd | Dry cell |
| US6104600A (en) * | 1998-02-02 | 2000-08-15 | Asahi Glass Company Ltd. | Electric double layer capacitor |
| CN110376816A (en) * | 2019-07-16 | 2019-10-25 | 西安交通大学 | Self-powered tungsten oxide base electrochromic device based on aluminium ion hydrogel and preparation method thereof |
| CN111600081A (en) * | 2020-06-02 | 2020-08-28 | 南开大学 | Rechargeable water-based zinc ion battery with wide temperature range and long cycle life |
| CN112255854A (en) * | 2020-11-06 | 2021-01-22 | 广西大学 | Zinc ion driven titanium dioxide electrochromic device and preparation method thereof |
-
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- 2021-08-26 CN CN202110985857.3A patent/CN113759625A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3905834A (en) * | 1968-08-08 | 1975-09-16 | Matsushita Electric Ind Co Ltd | Dry cell |
| US6104600A (en) * | 1998-02-02 | 2000-08-15 | Asahi Glass Company Ltd. | Electric double layer capacitor |
| CN110376816A (en) * | 2019-07-16 | 2019-10-25 | 西安交通大学 | Self-powered tungsten oxide base electrochromic device based on aluminium ion hydrogel and preparation method thereof |
| CN111600081A (en) * | 2020-06-02 | 2020-08-28 | 南开大学 | Rechargeable water-based zinc ion battery with wide temperature range and long cycle life |
| CN112255854A (en) * | 2020-11-06 | 2021-01-22 | 广西大学 | Zinc ion driven titanium dioxide electrochromic device and preparation method thereof |
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| CN114839818A (en) * | 2022-04-13 | 2022-08-02 | 西安交通大学 | Iron ion electrolyte tungsten oxide-based multicolor electrochromic device and preparation method and application thereof |
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