CN114675457A - Passive self-bias electrochromic intelligent window - Google Patents
Passive self-bias electrochromic intelligent window Download PDFInfo
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- CN114675457A CN114675457A CN202011574168.5A CN202011574168A CN114675457A CN 114675457 A CN114675457 A CN 114675457A CN 202011574168 A CN202011574168 A CN 202011574168A CN 114675457 A CN114675457 A CN 114675457A
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- G—PHYSICS
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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
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- 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
- 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
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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
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
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- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
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- Inorganic Chemistry (AREA)
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Abstract
The invention relates to a passive self-bias electrochromic intelligent window, which is provided with: the electrochromic device is provided with a first transparent electrode layer, an electrochromic layer for regulating and controlling visible light, an ion conducting layer, an ion storage layer and a second transparent electrode layer which are sequentially arranged, wherein the first transparent electrode layer is transparent conductive glass; and the power supply device is provided with an infrared absorption coating formed on the glass surface of the transparent conductive glass, and a thermoelectric conversion device which is fixed on the edge of the glass surface of the transparent conductive glass and converts the heat energy generated by the infrared absorption coating absorbing heat into electric energy, and the electrochromic window utilizes the converted electric energy to regulate and control visible light.
Description
Technical Field
The invention belongs to the field of energy-saving materials, and particularly relates to a passive self-bias visible light controlled electrochromic intelligent window.
Background
The energy is an important foundation for maintaining the sustainable development of national economy and guaranteeing the living standard of people's materials. Nowadays, the problems of energy shortage, environmental pollution and the like are becoming more severe, and scientists are also striving to find methods for energy conservation and consumption reduction while developing new energy. The building is one of the main places where people carry out production and living activities, the building energy consumption accounts for a large proportion in the total energy consumption of the production and living of people, and the energy consumption of the lighting and air conditioning system for improving the building comfort level accounts for more than 75 percent in the total energy consumption of the building. The energy consumption of the two parts is related to the door glass, so that the development of the architectural glass with the energy-saving effect is an important way for realizing the energy saving of buildings. Current architectural glass ways to control energy loss are static, such as Low-E glass with high reflectivity in the infrared band, which prevents infrared from passing through the window; the hollow glass reduces the heat conduction and radiation between the indoor and the outdoor by utilizing the low air heat conduction coefficient. However, the heat is scattered in the air, which causes a great amount of heat island effect in cities, and a great amount of energy is wasted while light pollution is generated.
Disclosure of Invention
The invention aims to solve the problem that in the prior art, huge energy waste exists in solar energy in building glass, and aims to provide a passive self-bias visible light regulation electrochromic intelligent window.
In a first aspect, the present invention provides an electrochromic window, comprising:
the electrochromic device is provided with a first transparent electrode layer, an electrochromic layer for regulating visible light, an ion conducting layer, an ion storage layer and a second transparent electrode layer which are sequentially arranged, wherein the first transparent electrode layer is transparent conductive glass (provided with a transparent conducting layer and a glass layer); and
a power supply unit having an infrared absorption coating formed on the glass surface of the transparent conductive glass, and a thermoelectric conversion device fixed to an edge of the glass surface of the transparent conductive glass and converting thermal energy generated by the infrared absorption coating absorbing heat into electric energy,
the electrochromic window utilizes the converted electrical energy to regulate visible light.
The passive self-biased visible light modulating electrochromic window (smart window) proposed in the present invention. The indoor lighting requirement is met, and meanwhile, energy waste can be avoided. The composite electrochromic window provided by the invention can be used as a glass window, so that the temperature of the surface of the glass window can be quickly reduced, the radiation of the glass window is reduced, and the indoor cold pressure is reduced. While the converted electrical energy is sufficient to control the electrochromic window. And the transmittance of the electrochromic intelligent window can be adjusted according to the intensity of the converted electric energy. When light is gradually enhanced, after heat absorbed by the infrared barrier coating is transferred to the hot end of the thermoelectric material and converted into electric energy, voltage is gradually increased, electrochromism is gradually changed in color under the driving of the voltage, and the visible light transmittance is gradually reduced. When no light is irradiated, the device gradually returns to a colorless state, that is, the visible light transmittance of the whole device gradually increases. For example, when the light is intense, more heat is absorbed, and therefore, the voltage generated is higher, and the transmittance of electrochromic visible light is reduced. When the illumination is weakened, the absorbed infrared rays are reduced, the conversion voltage of the thermoelectric device is reduced, and the transmittance of electrochromic visible light is gradually improved. Similar functionality can be achieved with the currently reported translucent solar cells in combination with high performance electrochromic windows, however we have found that the transmittance of the translucent solar cells is only around 25%. Typically, the maximum transmittance of electrochromic windows is around 74%. Therefore, the transmittance of the whole device is only about 20%, and the device cannot meet the requirements of actual life. The invention can adjust the transmittance of the electrochromic intelligent window according to the intensity of the converted electric energy. The passive self-bias visible light control electrochromic intelligent window is realized through the linkage of light, heat and electricity. The invention has simple structure and can meet the passive requirement of special environment. And the automatic adjustment of environmental response can be applied to the fields of camouflage, environmental protection, biology and the like. Therefore, the electrochromic window provided by the invention is not only beneficial to improving the comprehensive utilization of solar energy, but also capable of reducing the energy use pressure (such as indoor energy use pressure) due to the self passive and non-inductive automatic regulation performance, and meets the requirements of different application scenes.
The infrared absorption coating can comprise resin, an infrared absorption material and a heat conduction auxiliary agent, wherein the infrared absorption material and the heat conduction auxiliary agent are dispersed in the resin, the infrared absorption material is cesium-doped tungsten oxide nano powder, and the heat conduction auxiliary agent is silicon nitride and/or aluminum nitride nano particles. Therefore, the infrared absorption coating can realize the high-efficiency conversion of infrared light into heat (according to experiments, under the irradiation of standard sunlight, the temperature of the surface of the film can be increased to 75-85 ℃), has high visible light transmittance (which can reach more than 85%), and can effectively improve the comprehensive utilization of solar energy.
The content of the infrared absorption material in the infrared absorption coating (after complete curing) can be 0.2 wt.% to 0.8 wt.%, and the mass ratio of the infrared absorption material to the thermal conductivity aid can be (0.5-2): 1.
the heat conduction auxiliary agent can be silicon nitride and/or aluminum nitride nano powder with the diameter of 20-60 nm.
The infrared absorption material can be cesium-doped tungsten oxide nano powder with the doping proportion of 32-33% (mol ratio).
The thickness of the infrared absorption coating can be 80-200 μm.
The resin can be one or more of silicone resin, PMMA resin and acrylic resin. The resin may comprise 90-95% by mass of the infrared absorbing coating.
The ultraviolet absorption rate of the infrared absorption coating can be more than or equal to 95%, the visible light transmittance can be more than or equal to 85%, and the infrared blocking rate can be more than or equal to 80%. The hardness of the infrared absorption coating can be 5H or above, abrasion and scraping in outdoor use can be borne, and the service life of the device is prolonged.
The infrared absorption coating can be obtained by mixing an infrared absorption material, a thermal conductivity aid, a resin solution (resin slurry), a solvent and the like to prepare a coating precursor, coating and curing. High solid content silicone coatings can be selected, and the hardness after complete curing can reach 6H or even above.
Can be usedThe thermoelectric material is bismuth telluride (Bi)2Te3) The thermoelectric device is matched with the infrared absorption coating, so that the infrared light can be efficiently converted into electric quantity.
The electrochromic device can automatically adjust the transmittance of the intelligent window according to the environmental light intensity in a non-inductive way. The electrochromic layer may be made of WO3－x、MoO3－xOr TiO2And the like; the thickness thereof may be 300-500 nm. The material of the ion conducting layer can be lithium tantalate (LiTaO)3) The thickness thereof may be 500-1000 nm.
The visible light transmittance adjusting range of the electrochromic window can be 20-85%, and the cycle number can be more than or equal to 103Next, the process is carried out.
The electrochromic window can also be provided with an electric energy output device used for outputting the electric energy converted by the power generation component. Therefore, the converted electric energy can be used for charging the electric equipment.
In one embodiment, the first transparent electrode layer may be electrically connected to a P-junction of the thermoelectric conversion device, and the second transparent electrode layer may be electrically connected to an N-junction of the thermoelectric conversion device;
when light is gradually enhanced, heat absorbed by the infrared barrier coating is transferred to the hot end of the thermoelectric material and converted into electric energy, voltage is gradually increased, electrochromism is gradually changed in color under the driving of the voltage, and the visible light transmittance is gradually reduced to 20% from 85%. In the absence of light (e.g., at night), the device gradually returns to the colorless state, i.e., visible light transmittance gradually increases from 20% to 85%.
Drawings
Fig. 1 schematically illustrates an electrochromic window having an infrared absorbing coating in accordance with one embodiment of the present invention. A in fig. 1 shows a schematic view of the operation of a glazing; b in fig. 1 represents a schematic view of the device structure;
figure 2 shows the uv-vis-ir transmittance spectra of the electrochromic window of example 2;
figure 3 shows the sample and common glass surface temperature under the infrared camera for the electrochromic window of example 2.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
The present disclosure relates to a passive self-bias control visible light transmittance electrochromic smart window (hereinafter, sometimes referred to as "smart window" or "glass window") capable of automatically adjusting transmittance according to light intensity. The glazing comprises an electrochromic device, an infrared absorbing coating and a thermoelectric conversion device (thermoelectric device). The surface of the glass window is coated with the infrared absorption coating with proper thickness, so that infrared light in a solar spectrum can be fully absorbed and converted into heat, and the heat is converted into electric quantity through the thermoelectric conversion device. And adjusting the transmittance of the electrochromic intelligent window according to the intensity of the converted electric energy. The passive self-bias visible light control electrochromic intelligent window is realized through the linkage of light, heat and electricity. The invention organically combines the three components together, can more fully utilize solar energy without applying voltage by special equipment, and can autonomously change color according to the intensity of light. The invention has simple structure and can meet the passive requirement of special environment. And the automatic regulation of environmental response can be applied to the fields of camouflage, environmental protection, biology and the like.
Embodiment 1
The electrochromic window of the present embodiment includes an electrochromic device and a solar power supply device. The electrochromic device adopts a conventional structure electrochromic device with a first transparent electrode layer, an electrochromic layer for regulating visible light, an ion conducting layer, an ion storage layer and a second transparent electrode layer which are sequentially arranged. The first transparent electrode layer is made of transparent conductive glass and is provided with a transparent conductive layer and a glass layer. The transparent conductive glass selected by the present disclosure is not particularly limited, and transparent conductive glass known to those skilled in the art may be used, for example, FTO transparent conductive glass, ITO transparent conductive glass, AZO transparent conductive glass, ATO transparent conductive glass may be used. The thickness of the first transparent electrode layer may be 100-300 nm.
The electrochromic device can utilize the converted electric energy to regulate and control the visible light transmittance under different voltages. From the aspects of stability and response speed of the device under dynamically changing voltageWO can be adopted as the material of the electrochromic layer3－x、MoO3－xOr TiO2And the like; the thickness thereof may be 300-500 nm. The ion conducting layer may be lithium tantalate (LiTaO3) and may have a thickness of 500-1000 nm. The ion storage layer may be made of nickel oxide (NiOx). The thickness may be 60-200 nm. The first transparent electrode layer can be made of transparent conductive glass, and the thickness can be 500-1000 nm. The present disclosure does not particularly limit the method of preparing the electrochromic device, and methods well known to those skilled in the art may be employed. For example, the electrochromic device can be prepared by sequentially preparing an electrochromic layer, an ion conducting layer, an ion storage layer and a second transparent electrode layer on the surface of a first transparent electrode through a magnetron sputtering method.
The disclosed solar power supply device is provided with an infrared absorption coating and a thermoelectric conversion device. The infrared absorption coating is formed on the glass surface of the transparent conductive glass. The infrared absorption coating comprises resin, infrared absorption nano powder and a heat conduction auxiliary agent which are uniformly dispersed in the resin. The thickness of the infrared absorption coating can be 80-200 μm, which can ensure sufficient absorption of infrared light.
The thermal conductivity aid may include silicon nitride and/or aluminum nitride nanoparticles. The thermal conductivity of the resin coating can be improved by adding a proper thermal conductivity auxiliary agent, so that the heat converted by absorbing infrared light can be further sufficiently and timely transferred to a thermoelectric device, and the heat is converted into electric energy to be output. The nanoparticles may have a particle size of 20-60 nm. The heat conduction aid is preferably aluminum nitride because aluminum nitride has better heat conduction and excellent dispersibility in a solution, and has better heat conduction performance. The heat conduction auxiliary agent can account for 1-3 wt% of the completely cured coating, and can easily inhibit influence on visible light transmittance. In addition, the silicon nitride or aluminum nitride heat conduction aid is low in cost, and the silicon nitride or aluminum nitride nanoparticles can have good dispersibility in resin, so that the device is easy to have higher visible light transmittance.
The infrared absorbing material may be cesium-doped tungsten oxide nanopowder (in this embodiment, Cs of tungsten bronze phase is doped with WO)3Nanopowder). mid-IR of the IR-absorbing coating (fully cured coating)The content of the absorbing material can be 0.2 wt.% to 0.8 wt.%, and the insufficient influence on the visible light transmittance and the infrared blocking rate can be easily inhibited. The mass ratio of the infrared absorption material to the thermal conductivity aid may be (0.5-2): 1, the influence of too little heat conduction auxiliary agent on the heat conduction efficiency of the film can be inhibited, and the reduction of the visible light transmittance of the film along with the reduction of the dispersibility of the auxiliary agent caused by too high heat conduction auxiliary agent can be inhibited. Preferably, the mass ratio of the infrared absorption material to the heat conduction auxiliary agent is (0.5-1): 1, thereby further balancing visible light transmittance and infrared efficiency. In terms of energy absorption capability of the infrared light portion, the infrared absorbing material is preferably a cesium-doped tungsten oxide nanopowder having a doping ratio of 32 to 33% (molar ratio). The particle size of the infrared absorption material can be more than 10 nanometers and less than 100 nanometers, and when the particle size of the infrared absorption powder is dozens of nanometers, the infrared absorption powder is favorable for being dispersed in resin, can further inhibit the visible light transmittance of the whole film layer from being influenced by insufficient dispersion, and is easy to reduce the process difficulty.
The resin may be silicone resin, PMMA resin, acrylic resin, or the like. The infrared absorption coating can also be provided with a hardening agent, so that the hardness of the coating film at high temperature is improved, and the service life of the coating film at high temperature is prolonged.
The infrared absorption coating can be obtained by mixing an infrared absorption material, a thermal conductivity aid, a resin solution (resin slurry), a solvent and the like to prepare a coating precursor, coating and curing. The resin solution may use silicone, PMMA, acrylic resin, or the like. The solvent may be PMA, ethanol, toluene, DMF, NMP, isopropanol. High solid content (solid content is more than or equal to 95 wt.%) of the organosilicon coating is preferred, and the hardness can reach 6H or even above after complete curing. In some embodiments, the infrared absorbing material may comprise 0.3 wt% to 1 wt% of the total coating precursor, the resin paste may comprise 70 wt% to 85 wt% of the coating precursor, the solvent may comprise 10 wt% to 20 wt% of the coating precursor, and the thermal conductivity aid may comprise 1 wt% to 2 wt% of the coating precursor. It should be noted that after the resin slurry is completely cured on the surface of the substrate, the solvent is completely volatilized, so that the infrared absorbing material in the film after curing can account for 0.2-0.8 wt% of the total amount of the film, the resin slurry can account for 90-95 wt% of the film, and the heat conduction aid can account for 1-3 wt% of the film. The coating precursor may be mixed by any method known to those skilled in the art, such as by stirring. In the disclosure, the visible light transmittance of the infrared absorption layer can be more than or equal to 85%, and the infrared light blocking rate can be more than or equal to 80%. In addition, the UV absorption of the coating can be made to be 95% or more by adding 5-10 wt% of UV absorber (e.g., BASF 1120, BASF 292).
The coating precursor may be applied to the glass side of the (first conductive layer of the) electrochromic device by screen printing, spin coating, spray coating, doctor blading or pulling. For example, the glass can be made to have electrochromic devices on the outer surface (the side where the conductive layer is located, facing outdoors) and infrared absorbing materials and thermoelectric devices on the inner surface (facing indoors) in that order.
The thermoelectric conversion device is fixed on the edge of the glass surface of the transparent conductive glass and converts the heat energy generated by the infrared absorption coating absorbing heat into electric energy. A suitable number of devices may be selected to surround the glazing to take full advantage of the heat generated by the conversion of infrared light. For example, a ring of thermoelectric conversion devices may be arranged at the edge of the smart window. The thermoelectric conversion device is preferably made of bismuth telluride materials (commercial bismuth telluride materials can be used), and can be matched with the infrared absorption coating to realize high-efficiency conversion of infrared light into electric quantity. The thermoelectric conversion efficiency of the thermoelectric material can reach 0.8 percent in the range of normal temperature (0-100 ℃). Based on the device, under the standard sun, 10X 10cm2The device of (2) can realize reversible voltage output of 0-4V. The thermoelectric device may be bonded to the glazing in such a way that the hot end of the thermoelectric device is attached to the edge (peripheral surface) of the glazing and to the infrared absorbing coating, and the cold end is exposed to the air. The individual device dimensions may be, for example, standard dimensions 30mm x 34 mm. The solar power supply unit of the panel is electrically connected to the electrochromic device through, for example, a wire, and electrodes are connected to both poles of the electrochromic device.
And respectively connecting the P junction and the N junction of the thermoelectric device with the anode and the cathode of the electrochromic device (the P junction of the thermoelectric device leads out the anode, and the N junction of the thermoelectric device leads out the cathode). The heat absorbed by the lamp is more when the lamp is strongly illuminated, so the voltage generated is higher, and the transmittance of the electrochromic visible light is higherAnd decreases. When light is gradually enhanced, heat absorbed by the infrared barrier coating is transferred to the hot end of the thermoelectric material and converted into electric energy, voltage is gradually increased, electrochromism is gradually changed under the driving of the voltage, and the visible light transmittance is gradually reduced from 85% to 20%. For example, when light is not irradiated at night, the device gradually returns to a colorless state due to no applied voltage, that is, the visible light transmittance of the whole device gradually increases from 20% to 85%. Therefore, the light-heat-electricity linked passive self-bias visible light regulation and control electrochromic intelligent window can automatically regulate the transmittance of the intelligent window in a non-inductive manner according to the ambient light intensity. Moreover, the glass window can ensure high visible light transmittance, high infrared blocking rate, high-efficiency photo-thermal conversion efficiency and high-thermoelectric conversion efficiency. The visible light regulation rate of the electrochromic intelligent window can be 20-85%, and the electrochromic intelligent window can be ensured to meet the function of serving as an intelligent window or a photoelectric display sensor; the cycle number can be more than or equal to 10 3Next, the process is carried out. The visible light transmittance of the infrared absorption layer can be more than or equal to 85 percent, and the infrared light blocking rate can be more than or equal to 80 percent. The surface temperature of the glass window can be 75-85 ℃, and the thermoelectric conversion efficiency can be 0.5-1%. The obstruction to infrared light is more than or equal to 80 percent, namely the energy of the sunlight can be obstructed. The device can be used as a passive electrochromic device and can be used as a light sensor, the intensity of light at the moment is indicated by the depth of color change, the device is used as the passive light sensor, an external power supply is not needed, and the use of various scenes can be met; the intelligent window can be used as an intelligent window, the transmittance of visible light can be adjusted according to the intensity of light, and the comfort level of people in a room is improved.
Embodiment 2
Compared with embodiment 1, the electrochromic smart window of embodiment 2 further has an electric energy output device for outputting the electric energy converted by the power generation component. Therefore, the converted electric energy can be used for charging the electric equipment. The power generation assembly can further comprise an electric energy storage device for storing the electric energy converted by the power generation assembly for standby.
The beneficial effects of the invention also include:
the electrochromic intelligent window ensures high visible light transmittance and simultaneously fully isolates infrared light, thereby reducing the energy consumption of an indoor air conditioner;
The electrochromic intelligent window can realize the high-efficiency conversion of infrared light into heat and conduct the heat to thermoelectric devices around the glass window, thereby reducing the temperature of the surface of the glass and the radiance of the glass window;
the electrochromic intelligent window can realize passive and non-inductive automatic regulation of the visible light transmittance, and can meet the requirements of various scenes.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
In the following examples, reagents, materials and instruments used are all conventional reagents, conventional materials and conventional instruments, which are commercially available, if not specifically mentioned, and the reagents involved therein can also be synthesized by conventional synthesis methods.
Example 1
Preparing electrochromic glass on the surface of the ITO conductive glass through magnetron sputtering continuous deposition: respectively are tungsten oxide, lithium tantalate, nickel oxide and ITO transparent conductive electrodes. The method comprises the specific steps of ultrasonically cleaning a substrate (ITO glass) with acetone, ethanol and deionized water for 20min, fixing the substrate on a substrate tray with a high-temperature adhesive tape, putting the substrate on a sample chamber, pumping the substrate to below 5Pa by opening a mechanical pump, opening a baffle valve, and feeding the substrate into a sputtering chamber with the vacuum degree (background vacuum degree) of below 10-4 Pa. The metal nickel is used as a target material, pure argon and oxygen are introduced, the flow ratio is 96:4sccm, the pressure is 1.0Pa, the vertical distance between the target material and the substrate is 15cm, the temperature of the tray is kept at room temperature, a direct-current power supply (the power is 70W) is started, pre-sputtering is carried out for 5min, a baffle is started, and the lithium nickelate ceramic target material is sputtered for 30 min. And (3) taking a lithium tantalate ceramic target as a target material, introducing pure argon, wherein the pressure is 1.0Pa, the vertical distance between the target material and the substrate is 15cm, keeping the temperature of the tray at room temperature, starting a direct-current power supply (the power is 100W), pre-sputtering for 5min, starting a baffle, and sputtering the lithium nickelate ceramic target material for 90 min. And then, taking metal tungsten as a target, taking argon and oxygen as sputtering gases, setting the total pressure to be 2.0Pa, setting the oxygen partial pressure to be 6%, setting the distance between the target and the substrate to be 15cm, setting the initial substrate temperature to be room temperature, setting the power of a direct current power supply applied to the target to be 70W, and setting the deposition time to be 45 min. Finally, using ITO as a target material, introducing pure argon gas with the pressure of 0.3Pa, keeping the vertical distance between the target material and the substrate at 15cm, keeping the temperature of the tray at room temperature, starting a direct-current power supply (with the power of 100W), pre-sputtering for 5min, starting a baffle, and sputtering a lithium nickelate ceramic target material for 60 min;
Then coating resin material of infrared absorption coating on the glass surface of the ITO substrate, wherein the doping proportion is 33 percent of Cs-doped WO3The nano powder accounts for 0.6 percent (mass ratio) of the total amount of the coating precursor, the organic silicon resin slurry accounts for 76.5 percent (mass ratio) of the coating precursor, the aluminum nitride nano powder accounts for 1 percent (mass ratio) of the coating precursor, and the solvent adopts PMA (the balance being solvent). The glass window is coated on the surface of the glass window by a screen printing method, and the thickness of the film is about 80 mu m. Bi of standard size (30 mm. times.30 mm. times.34 mm)2Te3The hot end of the thermoelectric device is attached to the periphery of the surface of the glass window, and the cold end of the thermoelectric device is exposed in the air. And respectively connecting the P junction and the N junction of the thermoelectric device with the anode and the cathode of the electrochromic device.
Example 2
Electrochromic devices were prepared on ITO conductive glass according to the procedure in example 1. Then coating a resin material of an infrared absorption coating on the glass surface of the ITO substrate, wherein the Cs doping proportion is 33 percent of Cs doping WO3The nano powder accounts for 0.6 percent of the total amount of the coating precursor, the organic silicon resin slurry accounts for 76.5 percent of the coating precursor, the aluminum nitride nano powder accounts for 1 percent of the coating precursor, and the solvent adopts PMA. The coating is coated on the surface of the glass window by a screen printing method, and the thickness of the film is about 120 mu m. Bi of standard size (30 mm. times.30 mm. times.34 mm) 2Te3The hot end of the thermoelectric device being attached to the surface of the glazingFour weeks with the cold end exposed to air. And respectively connecting the P junction and the N junction of the thermoelectric device with the anode and the cathode of the electrochromic device.
Example 3
Electrochromic devices were prepared on ITO conductive glass according to the procedure in example 1. Then coating resin material of infrared absorption coating on the glass surface of the ITO substrate, wherein the doping proportion is 33 percent of Cs-doped WO3The nano powder accounts for 0.6 percent of the total amount of the coating precursor, the organic silicon resin slurry accounts for 76.5 percent of the coating precursor, the aluminum nitride nano powder accounts for 1 percent of the coating precursor, and the solvent adopts PMA. The glass window surface is coated by a screen printing method, and the thickness of the film is about 200 mu m. Bi of standard size (30 mm. times.30 mm. times.34 mm)2Te3The hot end of the thermoelectric device is attached to the periphery of the surface of the glass window, and the cold end of the thermoelectric device is exposed in the air. And respectively connecting the P junction and the N junction of the thermoelectric device with the anode and the cathode of the electrochromic device.
Example 4
Electrochromic devices were prepared on ITO conductive glass according to the procedure in example 1. Then coating resin material of infrared absorption coating on the glass surface of the ITO substrate, wherein the doping proportion is 33 percent of Cs-doped WO3The nano powder accounts for 0.6 percent of the total amount of the coating precursor, the organic silicon resin slurry accounts for 76.5 percent of the coating precursor, the silicon nitride nano powder accounts for 1 percent of the coating precursor, and the solvent adopts PMA. The glass window surface is coated by a screen printing method, and the thickness of the film is about 120 mu m. Bi of standard size (30 mm. times.30 mm. times.34 mm) 2Te3The hot end of the thermoelectric device is attached to the periphery of the surface of the glass window, and the cold end of the thermoelectric device is exposed in the air. And respectively connecting the P junction and the N junction of the thermoelectric device with the anode and the cathode of the electrochromic device.
Example 5
Electrochromic devices were prepared on ITO conductive glass according to the procedure in example 1. Then coating resin material of infrared absorption coating on the glass surface of the ITO substrate, wherein the doping proportion is 33 percent of Cs-doped WO3The nano powder accounts for 0.6 percent of the total amount of the coating precursor, the organic silicon resin slurry accounts for 76.5 percent of the coating precursor, the aluminum nitride nano powder accounts for 1.2 percent of the coating precursor, and the solvent adopts PMA. The glass window is coated on the surface of the glass window by a screen printing method,the film thickness was about 120 μm. Bi of standard size (30 mm. times.30 mm. times.34 mm)2Te3The hot end of the thermoelectric device is attached to the periphery of the surface of the glass window, and the cold end of the thermoelectric device is exposed in the air. And respectively connecting the P junction and the N junction of the thermoelectric device with the anode and the cathode of the electrochromic device.
Example 6
Electrochromic devices were prepared on ITO conductive glass according to the procedure in example 1. Then coating resin material of infrared absorption coating on the glass surface of the ITO substrate, wherein the doping proportion is 33 percent of Cs-doped WO3The nano powder accounts for 0.8 percent of the total amount of the coating precursor, the organic silicon resin slurry accounts for 76.5 percent of the coating precursor, the aluminum nitride nano powder accounts for 1 percent of the coating precursor, and the solvent adopts PMA. The glass window surface is coated by a screen printing method, and the thickness of the film is about 120 mu m. Bi of standard size (30 mm. times.30 mm. times.34 mm) 2Te3The hot end of the thermoelectric device is attached to the periphery of the surface of the glass window, and the cold end of the thermoelectric device is exposed in the air. And respectively connecting the P junction and the N junction of the thermoelectric device with the anode and the cathode of the electrochromic device.
Example 7
Electrochromic devices were prepared on ITO conductive glass according to the procedure in example 1. Then coating resin material of infrared absorption coating on the glass surface of the ITO substrate, wherein the doping proportion is 32% of Cs doped WO3The nano powder accounts for 0.6 percent of the total amount of the coating precursor, the organic silicon resin slurry accounts for 76.5 percent of the coating precursor, the aluminum nitride nano powder accounts for 1 percent of the coating precursor, and the solvent adopts PMA. The glass window surface is coated by a screen printing method, and the thickness of the film is about 200 mu m. Bi of standard size (30 mm. times.30 mm. times.34 mm)2Te3The hot end of the thermoelectric device is attached to the periphery of the surface of the glass window, and the cold end of the thermoelectric device is exposed in the air. And respectively connecting the P junction and the N junction of the thermoelectric device with the anode and the cathode of the electrochromic device.
The infrared transmittance is measured by an ultraviolet-visible-infrared spectrophotometer. The test results are shown in table 1.
TABLE 1
Fig. 3 shows the surface temperature of the sample and the ordinary glass under the infrared camera of the electrochromic window of example 2, and the surface temperature of the film after sufficient outdoor illumination is 82 ℃.
The infrared barrier material (comprising infrared absorption powder and heat conduction auxiliary agent) added in the method has low concentration, and aims to improve the visible light transmittance. The infrared blocking rate under the low thickness can be improved by improving the proportion of the infrared absorption powder. However, the thermal conductivity aid required to meet the requirements when the thickness of the film layer is low affects the visible light transmittance of the film layer. By regulating and controlling the thickness of the film layer, the infrared barrier material and the concentration of the infrared barrier material, the dual requirements of infrared barrier and visible transmission can be met. In the electrochromic window of the present disclosure, it is desirable that the thickness of the infrared absorption coating is 80 to 200 μm, and an increase in the thickness of the infrared absorption coating increases the barrier effect and correspondingly decreases the visible light transmittance. When the thickness of the film layer is further increased (more than 200 mu m), the visible light transmittance is influenced, and on the other hand, the process difficulty and the cost are increased. Further, the thinner the coating layer is, the less the infrared blocking effect becomes. Also, it is desirable that the thermal conductivity aid accounts for 1 to 3 wt% of the coating after complete curing, and an excessive amount of the thermal conductivity aid tends to lower the visible light transmittance, while an insufficient amount affects the thermal conductivity of the film, and ultimately the maximum output voltage. Compared with the doping amount of 33%, the 32% doping amount (cesium-doped tungsten oxide nano powder) has a weak photothermal conversion effect, and the generated temperature difference is small, so that the corresponding maximum output voltage is small.
Comparative example 1:
electrochromic devices were prepared on ITO conductive glass according to the procedure in example 1. Then coating a resin material of an infrared absorption coating on the glass surface of the ITO substrate, wherein the Cs doping proportion is 33 percent of Cs doping WO3The nano powder accounts for 0.6 percent of the total amount of the coating precursor, the organic silicon resin slurry accounts for 76.5 percent of the coating precursor, the PMA is a solvent, and the aluminum nitride nano powder accounts for 1 percent of the coating precursor. The glass window is coated on the surface of the glass window by a screen printing method, and the thickness of the film is about 50 mu m. Bi of standard size (30 mm. times.30 mm. times.34 mm)2Te3The hot end of the thermoelectric device is attached to the periphery of the surface of the glass window, and the cold endExposed to air. Connecting the P junction and the N junction of the thermoelectric device with the anode and the cathode of the electrochromic device respectively;
the comparative example reduces the thickness of the film layer, resulting in insufficient infrared blocking capability, i.e., weak infrared absorption capability, and difficulty in generating a desired driving voltage.
Comparative example 2:
electrochromic devices were prepared on ITO conductive glass according to the procedure in example 1. Then coating a resin material of an infrared absorption coating on the glass surface of the ITO substrate, wherein the Cs doping proportion is 33 percent of Cs doping WO3The nano powder accounts for 0.6 percent of the total amount of the coating precursor, the organic silicon resin slurry accounts for 76.5 percent of the coating precursor, the PMA is a solvent, and the silver nanowires account for 1 percent of the coating precursor. The glass window surface is coated by a screen printing method, and the thickness of the film is about 120 mu m. Bi of standard size (30 mm. times.30 mm. times.34 mm) 2Te3The hot end of the thermoelectric device is attached to the periphery of the surface of the glass window, and the cold end of the thermoelectric device is exposed in the air. Connecting the P junction and the N junction of the thermoelectric device with the anode and the cathode of the electrochromic device respectively;
although the silver nanowires in the comparative example have good thermal conductivity, the silver nanowires cannot be efficiently dispersed in the resin coating, the visible light transmittance is influenced by high scattering of the silver nanowires, the infrared blocking rate of the final device is about 82%, and the visible light transmittance is only 73%.
Comparative example 3:
electrochromic devices were prepared on ITO conductive glass according to the procedure in example 1. Then coating a resin material of an infrared absorption coating on the glass surface of the ITO substrate, wherein the Cs doping proportion is 25 percent of Cs doped WO3The nano powder accounts for 0.6 percent of the total amount of the coating precursor, the organic silicon resin slurry accounts for 76.5 percent of the coating precursor, the PMA is a solvent, and the aluminum nitride nano powder accounts for 1 percent of the coating precursor. The glass window surface is coated by a screen printing method, and the thickness of the film is about 120 mu m. Bi of standard size (30 mm. times.30 mm. times.34 mm)2Te3The hot end of the thermoelectric device is attached to the periphery of the surface of the glass window, and the cold end of the thermoelectric device is exposed in the air. Connecting a P junction and an N junction of the thermoelectric device with the anode and the cathode of the electrochromic device respectively;
the lower the Cs doping, the red shift of the infrared absorption edge occurs, i.e. the energy absorption capacity of the infrared part is reduced. The infrared light blocking rate of the infrared absorbing coating of comparative example 3 was 66%, and the infrared light blocking rate of the entire device was 68%.
Claims (10)
1. An electrochromic window, comprising: the electrochromic device is provided with a first transparent electrode layer, an electrochromic layer for regulating and controlling visible light, an ion conducting layer, an ion storage layer and a second transparent electrode layer which are sequentially arranged, wherein the first transparent electrode layer is transparent conductive glass; and the power supply device is provided with an infrared absorption coating formed on the glass surface of the transparent conductive glass, and a thermoelectric conversion device which is fixed on the edge of the glass surface of the transparent conductive glass and converts the heat energy generated by the infrared absorption coating absorbing heat into electric energy, and the electrochromic window utilizes the converted electric energy to regulate and control visible light.
2. The electrochromic window of claim 1, wherein the infrared absorbing coating comprises a resin, an infrared absorbing material dispersed in the resin, and a thermal conductivity aid, wherein the infrared absorbing material is cesium-doped tungsten oxide nanopowder, and the thermal conductivity aid is silicon nitride and/or aluminum nitride nanoparticles.
3. The electrochromic window of claim 2, wherein the infrared absorbing coating comprises 0.2wt.% to 0.8wt.% of the infrared absorbing material, and the mass ratio of the infrared absorbing material to the thermal conductivity aid is (0.5 to 2): 1.
4. The electrochromic window of claim 2 or 3, wherein the infrared absorbing material is cesium-doped tungsten oxide nanopowder with a doping ratio of 32-33%.
5. Electrochromic window according to any of claims 2-4, characterized in that the resin is one or several of silicone, PMMA, acrylic.
6. Electrochromic window according to any of claims 1 to 5, characterised in that the infrared-absorbing coating has a thickness of 80-200 μm.
7. Electrochromic window according to any of claims 1 to 6, characterised in that the material of the electrochromic layer is WO3－x、MoO3－xOr TiO2；
The material of the ion conducting layer is lithium tantalate.
8. The electrochromic window according to any one of claims 1 to 7, wherein the visible light transmittance of the electrochromic window is adjusted in the range of 20% to 85%, and the cycle number is not less than 103Next, the process is carried out.
9. The electrochromic window according to any one of claims 1 to 8, further comprising an electric power output device for outputting electric power converted by the power generation module.
10. A light sensor comprising the electrochromic window according to any one of claims 1 to 9.
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