CN115185132B - Multi-metal anode self-energy-multi-mode electrochromic device and preparation method thereof - Google Patents
Multi-metal anode self-energy-multi-mode electrochromic device and preparation method thereof Download PDFInfo
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- CN115185132B CN115185132B CN202210543868.0A CN202210543868A CN115185132B CN 115185132 B CN115185132 B CN 115185132B CN 202210543868 A CN202210543868 A CN 202210543868A CN 115185132 B CN115185132 B CN 115185132B
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- 239000002184 metal Substances 0.000 title claims abstract description 127
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 72
- 239000000463 material Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 24
- 238000004528 spin coating Methods 0.000 claims abstract description 12
- 238000004806 packaging method and process Methods 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims description 16
- 238000004040 coloring Methods 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 10
- 239000003292 glue Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- 238000005265 energy consumption Methods 0.000 claims description 6
- 239000002159 nanocrystal Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000005562 fading Methods 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 230000033116 oxidation-reduction process Effects 0.000 claims description 2
- 238000002256 photodeposition Methods 0.000 claims description 2
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- 239000007787 solid Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010409 thin film Substances 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 3
- 230000009977 dual effect Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract 1
- 238000002834 transmittance Methods 0.000 description 16
- 239000002064 nanoplatelet Substances 0.000 description 11
- 229910006404 SnO 2 Inorganic materials 0.000 description 9
- 239000011888 foil Substances 0.000 description 9
- 238000001354 calcination Methods 0.000 description 6
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 6
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 238000004061 bleaching Methods 0.000 description 4
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- 239000002131 composite material Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
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- 239000004202 carbamide Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 239000004984 smart glass Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/163—Operation of electrochromic cells, e.g. electrodeposition cells; Circuit arrangements therefor
-
- 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
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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
- G02F1/1524—Transition metal compounds
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/153—Constructional details
- G02F1/155—Electrodes
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- 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
- G02F2001/15145—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 the electrochromic layer comprises a mixture of anodic and cathodic compounds
Abstract
The application discloses a multi-metal anode self-energy-multi-mode electrochromic device and a preparation method thereof, wherein the preparation method is as follows: cleaning and airing the first conductive substrate and the second conductive substrate; growing a dual band electrochromic material on a second conductive substrate by a method including, but not limited to, spin coating, hydrothermal, or magnetron sputtering; adhering a metal A and a metal B to two sides of one side of the first conductive substrate; and taking the second conductive substrate loaded with the double-band electrochromic material as a working electrode, taking the first conductive substrate attached with the metal A and the metal B as a metal anode, and finally injecting electrolyte and packaging the device. The application aims to respectively combine the thin film cathode material with different metal anodes to generate open-circuit voltages with different magnitudes, and realize multiple modes by the built-in voltages so as to dynamically modulate the transmission degrees of visible light and near infrared light.
Description
Technical Field
The application belongs to the technical field of electrochromic, and particularly relates to a multi-metal anode self-energy-multi-mode electrochromic device and a preparation method thereof.
Background
The electrochromic technology refers to the phenomenon that the optical properties of materials change reversibly under the action of an external electric field, and the intelligent window prepared from the electrochromic materials has excellent capability of dynamically adjusting indoor light and temperature and has wide application prospect in the fields of commercial and civil buildings, automobiles and aerospace. In the solar spectrum, the near infrared band accounts for about 50% of the total solar radiation, so dynamic or selective modulation of near infrared light through electrochromic smart windows can have a significant impact on building thermal management, energy consumption, and comfort for indoor personnel. However, a common electrochromic smart window is mainly focused on the visible light region. Therefore, developing a dual-band electrochromic intelligent window, namely independently adjusting the transmittance of visible light and near infrared light, has important practical significance and scientific value.
Research shows that monoclinic crystal WO 3-x The transmittance of visible light and near infrared light can be independently controlled through local surface plasmon resonance and phase change conversion, respectively. Thereafter, dual band electrochromic materials controlling visible light and near infrared light are widely studied. Thus, electrochromic smart windows assembled from dual band electrochromic materials are capable of operating in three specific modes. The "bright" mode allows visible light and near infrared light to pass, the "cold" mode blocks most of near infrared light and allows visible light to pass, and the "dark" mode blocks visible light and near infrared light simultaneously. Furthermore, most reported electrochromic devices require an external power source to drive the change in optical transparency, which can hamper the independence and portability of these devices. Therefore, the dual-band electrochromic material and the anode metal are integrated into a multi-metal anode self-energy-multi-mode electrochromic device, different metal anodes are connected with the film cathode to generate open-circuit voltages with different magnitudes, when the open-circuit voltages are smaller, only positive ions in the electrolyte are driven to gather on the surface of the film cathode, and due to the effect of capacitive adsorption, the transmittance of the film cathode in the near infrared region is greatly reduced, and the transmittance of the visible light region is still kept at a higher level. When the open circuit voltage is large, most of cations in the electrolyte are strongly driven to be inserted into the thin film cathode, the crystal form of the cathode material is changed, and the transmittance in the visible light region can be adjusted.
While the operation of conventional electrochromic devices requires an external voltage to trigger the coloring/bleaching process, the coloring process of self-powered-multi-mode electrochromic devices achieves coloring by built-in voltage, and the energy consumption of the bleaching process can be partially recovered by powering other small devices. Therefore, the multi-metal anode self-energy-multi-mode electrochromic device is developed by combining the unique advantages of the self-power supply system and the dual-band electrochromic material, and has a certain prospect in popularization and application of the dual-band electrochromic intelligent window.
Disclosure of Invention
While the operation of conventional electrochromic devices requires an external voltage to trigger the coloring/bleaching process, the coloring process of self-powered-multi-mode electrochromic devices achieves coloring by built-in voltage, and the energy consumption of the bleaching process can be partially recovered by powering other small devices. Aiming at the defects of the prior art, the application provides a preparation method of a multi-metal anode self-energy-multi-mode electrochromic device, and the multi-metal anode self-energy-multi-mode electrochromic device obtained according to the preparation method.
The technical scheme is as follows:
a multi-metal anode self-energy-multi-mode electrochromic device comprises a first conductive substrate, a metal A, a metal B, an electrolyte, a material C and a second conductive substrate; the metal A and the metal B are respectively adhered to two sides of one side of the first conductive substrate to form a metal anode; material C is formed above the second conductive substrate and is used as a working electrode; electrolyte is injected between the metal anode and the working electrode, and the multi-metal anode self-energy-multi-mode electrochromic device is obtained; when the metal A and the material C are connected through a wire, the magnitude of an open-circuit voltage generated in the circuit is between 0 and 1V, and the electrochromic device is driven to be in a cooling mode by smaller voltage; when the metal B and the material C are connected through a wire, the magnitude of an open-circuit voltage generated in the circuit is 1-3V, and the electrochromic device is driven to be in a 'dark' mode by the larger voltage.
Further, because of the oxidation-reduction potential difference between the metal A, the metal B and the material C, an external circuit is formed after the metal A and the material C are connected by a wire, the material C is colored, and meanwhile, the external circuit has current, so that a discharging process is realized, and the external current can supply power for an externally connected electric device with the voltage lower than 0.5V; when a voltage of 3V is applied, ions are separated from a working electrode of the electrochromic device, so that a self-charging process is realized, meanwhile, a material C starts to fade, the device returns to an initial potential difference with high potential on one side and low potential on the other side, so that energy circulation is formed, the coloring process realizes coloring through built-in voltage, and energy consumption in the fading process realizes energy recovery through supplying power to other small devices.
Further, the first conductive substrate is FTO, ITO conductive glass or common transparent substrate material.
Further, the materials of the metal A and the metal B include, but are not limited to, cu, al, fe, zn, mg, and the metal A and the metal B are made of different metal materials so as to ensure that the open circuit voltage is in a proper voltage range; the area of the metal A and the metal B is 1/5-1/6 of that of the first conductive substrate, and the distance between the metal A and the metal B is greater than 2/3 of the width of the first conductive substrate.
Further, the electrolyte is solely in the form of a liquid, colloid or solid; the electrolyte includes, but is not limited to, H + 、Li + 、K + And Na (Na) + Monovalent ions or Mg 2+ 、Al 3+ 、Zn 2+ One or more of multivalent ions, and the concentration of the electrolyte is 0.5 mol/L-1 mol/L.
Further, said material C includes, but is not limited to, WO 3-x 、TiO 2-x Nanocrystals or ITO nanocrystals, where WO 3-x 、TiO 2-x The value range of the nanocrystal x is 0-1, and the thickness of the material C is 200-800 nm.
Further, the second conductive substrate includes, but is not limited to, FTO, ITO conductive glass, or flexible PET conductive film.
A method for preparing a multi-metal anode self-powered-multi-mode electrochromic device, comprising the steps of:
s1, cleaning and airing a first conductive substrate and a second conductive substrate;
s2, growing a material C on a second conductive substrate by a method including but not limited to photo-deposition, spin coating, hydrothermal or magnetron sputtering to serve as a working electrode;
s3, adhering metal A and metal B to two sides of one side of the first conductive substrate respectively to serve as a metal anode;
s4, separating the working electrode in the step S2 and the metal anode in the step S3 through a hollow PET gasket, leaving a small hole at the edge of the PET, packaging the device by ultraviolet curing glue, then injecting electrolyte into the small hole, and finally packaging the small hole by ultraviolet curing glue to obtain the multi-metal anode self-energy-multi-mode electrochromic device.
The beneficial effects are that:
1. the metallic anode employed in the present application allows the build-up of an intrinsic potential (controlled by the gibbs free energy difference between the given metallic anode and cathode materials) to drive the spontaneous coloration of the cathode electrochromic layer, thus eliminating the need for an external power source.
2. The application adopts the principle of a primary battery, so that the device only consumes unidirectional energy in the process of back and forth coloring/fading, and the consumed energy can be partially recovered through a discharging process, thereby supplying power to small-sized equipment such as a small bulb and the like.
3. The method adopts a multi-metal anode coupling regulation and control method, and achieves two modes of cooling and darkness by switching different metal anodes. When the thin film cathode is connected to the anode metal a (e.g., al), its open circuit voltage is greater than that when the thin film cathode is connected to the anode metal B (e.g., cu). Therefore, the transmittance of visible light and near infrared light can be dynamically regulated, and the preparation of the multi-mode and low-energy-consumption electrochromic device is truly realized.
Drawings
Fig. 1 is a schematic structural view of an electrochromic device prepared in example 1;
FIG. 2 is a graph of UV-vis-NIR transmittance at three different voltages for the electrochromic device prepared in example 1;
FIG. 3 is SnO prepared in example 1 2 Nanoplatelets and crystalline state WO 3-x Cross-sectional SEM characterization of the composite material of (a);
FIG. 4 shows SnO prepared in example 1 2 Nanoplatelets and crystalline state WO 3-x XRD characterization of the composite material of (2).
The reference numerals: 1-a first conductive substrate, 2-metal a, 3-metal B, 4-electrolyte, 5-material C, 6-a second conductive substrate.
Detailed Description
The application is further described with reference to the accompanying drawings and examples:
example 1
As in figure 1As shown, the multi-metal anode self-powered-multi-mode electrochromic device described herein comprises a first conductive substrate 1, a metal A2, a metal B3, an electrolyte 4, a material C5, and a second conductive substrate 6; the metal A2 and the metal B3 are respectively adhered to two sides of one side of the first conductive substrate 1 to form a metal anode; material C5 is formed over the second conductive substrate 6 as a working electrode; electrolyte 4 is injected between the metal anode and the working electrode, and metal A2, metal B3 and material C5 are respectively connected through wires; the first conductive substrate 1 is FTO glass, the metal A2 is Cu foil, the metal B3 is Al foil, and the electrolyte 4 is 1M AlCl 3 /ZnSO 4 Electrolyte, material C5 is SnO 2 Nanoplatelets and crystalline state WO 3-x The second conductive substrate 6 is FTO glass.
A method for preparing a multi-metal anode self-energy-multi-mode electrochromic device comprises the following steps,
s1 FTO conductive glass (2×3 cm) to be used as the first conductive substrate 1 and the second conductive substrate 6 2 ) Cleaning and airing;
s2 0.5g of urea was dissolved in 40 mL deionized water, followed by 10. Mu.L of thioglycolic acid and 0.5 mL of 37% HCl, and finally 0.05 g of SnCl 2 ·2H 2 O, stirring in air for 5 min to form a clear solution; then transferring into polytetrafluoroethylene lining with second conductive substrate 6, placing the conductive surface of second conductive substrate 6 downward at 45 deg. angle, reacting at 130deg.C for 8 h, taking out, cleaning, calcining at 400 deg.C for 3 h to obtain load SnO 2 A second conductive substrate 6 of nanoplatelets; weighing 0.4 g tungsten hexachloride powder, dissolving in 4 mL absolute ethyl alcohol, uniformly mixing, and spin-coating on long-standing SnO by using a spin-coating instrument 2 Irradiating the second conductive substrate 6 with ultraviolet lamp box for 5-10 min, repeating spin coating and irradiation for 6 times, and calcining at 400-500 deg.C for 1 h to obtain WO 3-x /SnO 2 A structure;
s3, shearing 1/5-1/6 of the area of the first conductive substrate 1 by the metal A2 and the metal B3, and adhering the two sides of one side of the first conductive substrate 1, wherein the interval distance between the metal A2 and the metal B3 is larger than the width 2/3 of the first conductive substrate 1;
s4 the step S2 is performed on SnO 2 Crystalline state WO on nanoplatelets 3-x The second conductive substrate 6 of (2) is used as a working electrode, the first conductive substrate 1 adhered with the metal A2 and the metal B3 in the step S3 is a metal anode, a PET gasket with the thickness of 0.2 and mm is cut into a hollow structure to separate the working electrode and the metal anode, a small hole is reserved at the edge of the PET, the device is packaged by ultraviolet curing glue, and then the small hole is smaller than Kong Zhuman M AlCl 3 /ZnSO 4 Electrolyte (AlCl) 3 :ZnSO 4 =1:1), and finally packaging the small holes with ultraviolet curing glue to obtain the electrochromic device.
Example 1 packaged electrochromic device using 1M AlCl 3 /ZnSO 4 Electrolyte is injected into the electrochromic device, and the UV-vis-NIR transmittance curves at three different voltages are shown in FIG. 2, when the working electrode is connected with metal A2 (Cu), the device is in a 'cool' mode, allowing visible light in sunlight to enter, shielding near infrared light (73.4% transmittance at 633 nm, 12.1% and 10.9% transmittance at 1200 nm and 1600 nm); when the working electrode is connected to metal B3 (Al), the device is in "dark" mode, shielding visible as well as near infrared light in sunlight (transmittance at 633 nm is 2.9%, transmittance at 1200 nm and 1600 nm is 0.7% and 1.1%); after a reverse +3.0V voltage, the device was in "bright" mode, allowing visible and near infrared light to pass through (85.4% transmittance at 633 nm, 74.8% and 86.6% transmittance at 1200 nm and 1600 nm).
SnO prepared in example 1 2 Nanoplatelets and crystalline state WO 3-x SEM characterization of the cross-section of the composite material of (2) is shown in figure 3, and it can be seen that the underlying SnO 2 The nano-sheets vertically grow on the FTO glass and have the length of about 300 percent nm and have cross-linked and open frames, which are beneficial to supporting WO 3-x Is a crystalline structure of the upper layer of the crystal form WO 3-x 。
SnO prepared in example 1 2 Nanoplatelets and crystalline state WO 3-x XRD characterization of the composite material of (2) is shown in FIG. 4, snO 2 The nano sheet is of tetragonal rutile structure, and the upper WO (WO) 3-x Is of a monoclinic crystal structure.
The bistable performance of the electrochromic device packaged in example 1 under different modes is characterized, and the bistable performance is another performance index of the electrochromic material. The excellent bi-stability indicates that power is only required between mode switches, and that power is not required to maintain its own color after the voltage is removed, greatly reducing power consumption. After the cathode is connected 250 to the different metal s, the transmittance after the loop state is disconnected changes. The transmittance at 1100 nm ("cold" mode) and 633 nm ("dark" mode) varied by 1.0% and 2.2% within 3600 s, respectively.
Example 2
A method for preparing a multi-metal anode self-energy-multi-mode electrochromic device comprises the following steps,
s1 FTO conductive glass (2×3 cm) to be the first conductive substrate 1 and the second conductive substrate 6 2 ) Cleaning and airing;
s2 0.5g of urea was dissolved in 40 mL deionized water, followed by 10. Mu.L of thioglycolic acid and 0.5 mL of 37% HCl, and finally 0.05 g of SnCl 2 ·2H 2 O, stirring for 5 min in air to form a clear solution, transferring into a polytetrafluoroethylene lining with a second conductive substrate 6, placing the conductive surface of the second conductive substrate 6 downwards at an angle of 45 DEG on the lining, reacting at 130 ℃ for 10 h, taking out, cleaning, calcining at 400 ℃ for 3 h to obtain the loaded SnO 2 A second conductive substrate 6 of nanoplatelets; weighing 0.4 g tungsten hexachloride powder, dissolving in 4 mL absolute ethyl alcohol, uniformly mixing, and spin-coating on long-standing SnO by using a spin-coating instrument 2 Irradiating the second conductive substrate 6 with ultraviolet lamp box for 5-10 min, repeating spin coating and irradiation for 6 times, and calcining at 400-500 deg.C for 1 h to obtain WO 3-x /SnO 2 A structure;
s3, shearing metal A2 (Al foil) and metal B3 (Zn foil) to 1/5-1/6 of the area of the first conductive substrate 1, and adhering the metal A2 (Al foil) and the metal B3 (Zn foil) to two sides of one side of the first conductive substrate 1, wherein the interval distance between the metal A2 and the metal B3 is larger than the width 2/3 of the first conductive substrate 1;
packaging of the S4 device: in step S2, snO 2 Crystalline state WO on nanoplatelets 3-x Is used as the second conductive substrate 6 of (2)In step S3, the first conductive substrate 1 adhered with the metal foil is used as a metal anode, a PET gasket with the thickness of 0.2 mm is cut into a hollow structure to separate the working electrode from the metal anode, a small hole is reserved at the edge of the PET, the device is packaged by ultraviolet curing glue, and then the metal anode is small Kong Zhuman M AlCl 3 Electrolyte (AlCl) 3 /ZnSO 4 And the ratio of the ultraviolet curing adhesive to the electrochromic device is 1:0), and finally, the small holes are encapsulated by the ultraviolet curing adhesive to obtain the electrochromic device.
Example 3
A method for preparing a multi-metal anode self-energy-multi-mode electrochromic device comprises the following steps,
s1 FTO conductive glass (2×3 cm) to be the first conductive substrate 1 and the second conductive substrate 6 2 ) Cleaning and airing;
s2 0.5g of urea was dissolved in 40 mL deionized water, followed by 10. Mu.L of thioglycolic acid and 0.5 mL of 37% HCl, and finally 0.05 g of SnCl 2 ·2H 2 O, stirring in air for 5 min to form clear solution. Then transferring into polytetrafluoroethylene lining with second conductive substrate 6, placing the conductive surface of second conductive substrate 6 downward at 45 deg. angle, reacting at 130 deg. C6 h, taking out and cleaning, calcining at 400 deg. C3 h to obtain load SnO 2 A second conductive substrate 6 of nanoplatelets; weighing 0.4 g tungsten hexachloride powder, dissolving in 4 mL absolute ethyl alcohol, uniformly mixing, and spin-coating on long-standing SnO by using a spin-coating instrument 2 Irradiating the second conductive substrate 6 with ultraviolet lamp box for 5-10 min, repeating spin coating and irradiation for 6 times, and calcining at 400-500 deg.C for 2 h to obtain WO 3-x /SnO 2 A structure;
s3, shearing metal A2 (Zn foil) and metal B3 (Cu foil) to 1/5-1/6 of the area of the first conductive substrate 1, and adhering the metal A2 (Zn foil) and the metal B3 (Cu foil) to two sides of one side of the first conductive substrate 1, wherein the interval distance between the metal A2 and the metal B3 is more than 2/3 of the width of the first conductive substrate 1;
packaging of the S4 device: in step S2, snO 2 Crystalline state WO on nanoplatelets 3-x As a working electrode, the first conductive substrate 1 with the metal foil adhered thereto in step S3 serves as a metal anodeA PET gasket with the thickness of 0.2 and mm is cut into a hollow structure to separate a working electrode and a metal anode, a small hole is reserved at the edge of the PET, an ultraviolet curing adhesive is used for packaging the device, and then a small Kong Zhuman M ZnSO is arranged from the small Kong Zhuman M ZnSO 4 Electrolyte (AlCl) 3 :ZnSO 4 =0:1), and finally packaging the small holes with ultraviolet curing glue to obtain the electrochromic device.
Claims (7)
1. A multi-metal anode self-powered-multi-mode electrochromic device characterized by: comprises a first conductive substrate (1), a metal A (2), a metal B (3), an electrolyte (4), a material C (5) and a second conductive substrate (6); the metal A (2) and the metal B (3) are respectively adhered to two sides of one side of the first conductive substrate (1) to form a metal anode; the material C (5) is formed above the second conductive substrate (6) and is used as a working electrode; injecting electrolyte (4) between the metal anode and the working electrode to obtain the multi-metal anode self-energy-multi-mode electrochromic device;
when the metal A (2) is connected with the material C (5) through a wire, the magnitude of an open-circuit voltage generated in the circuit is between 0 and 1V, and the electrochromic device is driven to be in a cooling mode by smaller voltage;
when the metal B (3) is connected with the material C (5) through a wire, the magnitude of an open-circuit voltage generated in the circuit is 1-3V, and the larger voltage drives the electrochromic device to be in a 'dark' mode;
when the metal A (2) or the metal B (3) and the material C (5) are connected through a wire, after +3. V voltage is reversely applied, the applied voltage drives the electrochromic device to be in a bright mode;
the material C (5) is WO 3-x 、TiO 2-x Nanocrystals or ITO nanocrystals, wherein X ranges from 0 to 1; the thickness of the material C (5) is 200-800 nm.
2. A multi-metal anode self-powered-multi-mode electrochromic device as defined in claim 1, wherein: because of the oxidation-reduction potential difference between the metal A (2), the metal B (3) and the material C (5), an external circuit is formed after the metal A (2) and the material C (5) are connected by a wire, the material C (5) is colored, and meanwhile, the external circuit has current, so that a discharging process is realized, and the external current can supply power for an externally connected electric device lower than 0.5V; when a voltage of 3V is applied, ions are separated from the working electrode of the electrochromic device, so that a charging process is realized, meanwhile, the material C (5) starts to fade, the device returns to an initial potential difference with high potential on one side and low potential on the other side, so that energy circulation is formed, the coloring process realizes coloring through built-in voltage, and energy consumption in the fading process realizes energy recovery through supplying power to other small devices.
3. A multi-metal anode self-powered-multi-mode electrochromic device as defined in claim 1, wherein: the first conductive substrate (1) is FTO, ITO conductive glass or common transparent substrate material.
4. A multi-metal anode self-powered-multi-mode electrochromic device as defined in claim 1, wherein: the materials of the metal A (2) and the metal B (3) are Cu, al, fe, zn or Mg, and the metal A (2) and the metal B (3) are made of different metal materials so as to ensure that the open circuit voltage is in a proper voltage range; the area of the metal A (2) and the area of the metal B (3) are 1/5-1/6 of that of the first conductive substrate (1), and the distance between the metal A and the metal B is larger than 2/3 of the width of the first conductive substrate (1).
5. A multi-metal anode self-powered-multi-mode electrochromic device as defined in claim 1, wherein: the electrolyte (4) is solely in the form of a liquid, a colloid or a solid; the electrolyte (4) contains H + 、Li + 、K + And Na (Na) + Monovalent ions or Mg 2+ 、Al 3+ 、Zn 2+ One or more of multivalent ions, and the concentration of the electrolyte is 0.5 mol/L-1 mol/L.
6. A multi-metal anode self-powered-multi-mode electrochromic device as defined in claim 1, wherein: the second conductive substrate (6) is FTO, ITO conductive glass or flexible PET conductive film.
7. A method of making a multi-metal anode self-powered-multi-mode electrochromic device according to claim 1, wherein: the method comprises the following steps: s1, cleaning and airing a first conductive substrate (1) and a second conductive substrate (6); s2 growing a material C (5) on a second conductive substrate (6) by a method including, but not limited to, photo-deposition, spin-coating, hydrothermal or magnetron sputtering, as a working electrode;
s3, adhering the metal A (2) and the metal B (3) to two sides of one side of the first conductive substrate (1) respectively to serve as a metal anode;
s4, separating the working electrode in the step S2 and the metal anode in the step S3 through a hollow PET gasket, leaving a small hole at the edge of the PET, packaging the device by ultraviolet curing glue, then injecting electrolyte (4) into the small hole, and finally packaging the small hole by ultraviolet curing glue to obtain the multi-metal anode self-energy-multi-mode electrochromic device.
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| PCT/CN2022/107419 WO2023221288A1 (en) | 2022-05-19 | 2022-07-22 | Multi-metal anode self-powered-multi-modal electrochromic device and preparation method |
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| CN109661611A (en) * | 2016-10-10 | 2019-04-19 | 金泰克斯公司 | Polarizing window sub-assembly |
| CN110720120A (en) * | 2017-04-26 | 2020-01-21 | 唯景公司 | Tintable window system for building services |
| CN111386193A (en) * | 2018-10-26 | 2020-07-07 | 法国圣戈班玻璃厂 | Composite glass pane comprising a functional element with electrically controllable optical properties which can be switched in a segment-like manner |
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| CA3035398A1 (en) * | 2019-03-01 | 2020-09-01 | Abdulhakem Elezzabi | Electrochromic device |
| CN111638618A (en) * | 2020-07-01 | 2020-09-08 | 京东方科技集团股份有限公司 | Dimming panel, dimming glass, dimming device and light transmittance adjusting system |
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| CN109661611A (en) * | 2016-10-10 | 2019-04-19 | 金泰克斯公司 | Polarizing window sub-assembly |
| CN110720120A (en) * | 2017-04-26 | 2020-01-21 | 唯景公司 | Tintable window system for building services |
| CN111386193A (en) * | 2018-10-26 | 2020-07-07 | 法国圣戈班玻璃厂 | Composite glass pane comprising a functional element with electrically controllable optical properties which can be switched in a segment-like manner |
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| Novel triazine-centered viologen analogues for dual-band electrochromic devices;WU Nan等;《SOLAR ENERGY MATERIALS AND SOLAR CELLS》;第195卷;117-120 * |
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