CN111650795B

CN111650795B - Electrochromic glass

Info

Publication number: CN111650795B
Application number: CN202010570393.5A
Authority: CN
Inventors: 刘江; 王群华; 吉顺青
Original assignee: Nantong Fanhua New Material Technology Co ltd; Jiangsu Prosperous Yingcai Technology Co ltd
Current assignee: Nantong Fanhua New Material Technology Co ltd; Jiangsu Prosperous Yingcai Technology Co ltd
Priority date: 2020-06-19
Filing date: 2020-06-19
Publication date: 2025-03-11
Anticipated expiration: 2040-06-19
Also published as: CN111650795A

Abstract

The present invention discloses an electrochromic glass, which relates to the field of electrochromism, and includes a substrate, wherein the substrate includes a first substrate and a second substrate, wherein an electrochromic device is provided between the first substrate and the second substrate, wherein the electrochromic device is provided with a first conductive layer, an electrochromic layer, an ion conduction layer, an ion storage layer, and a second conductive layer in sequence starting from the first substrate; an electrode, wherein the electrode is provided to supply power to the electrochromic device; and the inner surface of the substrate includes a groove, wherein the groove is opposite to the electrode, the depth of the groove is less than the thickness of the substrate, and the periphery of the groove and the periphery of the substrate are sealed by edge sealing materials. The technical effect of the present invention is that the product is highly integrated, and a series of control or communication units can be additionally integrated, thereby increasing the product life after glass encapsulation.

Description

Electrochromic glass

Technical Field

The invention relates to the field of electrochromic, in particular to electrochromic glass.

Background

Electrochromic refers to a phenomenon in which optical properties (reflectivity, transmittance, absorptivity, etc.) change stably and reversibly under the action of an applied electric field. Electrochromic technology has been developed for forty years, and electrochromic devices (Electrochromic Device, ECD) have wide application prospects in the fields of intelligent windows, displays, spacecraft temperature control modulation, automobile dizzy-free rearview mirrors, weapon equipment stealth and the like due to the characteristics of continuous adjustability of transmitted light intensity, low energy loss, open-circuit memory function and the like. The ECD-based glass is used as a brand new intelligent window, the intensity of incident sunlight can be regulated according to comfort requirements, the energy consumption is effectively reduced, and a remarkable energy-saving effect is shown. With the continuous improvement of human requirements on consumption products, ECD shows huge market prospect and application value in the fields of automobiles, household appliances, aerospace, rail transit, green buildings and the like, and electrochromic products are the new generation of high-efficiency building energy-saving products after heat absorption glass, heat reflection coated glass and low-radiation glass, which are most widely paid attention to and paid attention to at home and abroad.

At present, the existing electrochromic products mainly adopt hollow encapsulation, and in the encapsulation process, bus bars, wires and the like need to be penetrated through the hollow encapsulation structure to be connected with electrochromic devices, so that the sealing performance of the hollow electrochromic products can be seriously affected. There is a risk of durability failure of sealing performance in both printing silver paste and bus bars, and once hollow encapsulation failure occurs, the cycle life of electrochromic products is greatly affected, and even damage is possible.

Disclosure of Invention

In view of the above-mentioned drawbacks of the prior art, the present invention aims to improve the reliability of the encapsulation of electrochromic products, conceal the electrodes and improve the aesthetic appearance.

In order to achieve the aim, the invention provides electrochromic glass, which comprises a substrate, wherein the substrate comprises a first substrate and a second substrate, an electrochromic device is arranged between the first substrate and the second substrate, a first conductive layer, an electrochromic layer, an ion conducting layer, an ion storage layer and a second conductive layer are sequentially arranged from the first substrate, electrodes are arranged for supplying power to the electrochromic device, the inner surface of the substrate comprises a notch, the notch is opposite to the electrodes, the depth of the notch is smaller than the thickness of the substrate, and the periphery of the notch and the periphery of the substrate are sealed by edge sealing materials.

Further, the notch groove comprises a drying body.

Further, the drying body is one or more of molecular sieve, silica gel and active alumina.

Further, the electrode comprises a first electrode and a second electrode, the first electrode is in electrical contact with the first conductive layer, the second electrode is in electrical connection with the second conductive layer, the first electrode is located in the notch of the inner surface of the first substrate, and the width of the first electrode corresponds to the width of the notch of the inner surface of the first substrate.

Further, the electrochromic device further comprises an ion blocking layer, wherein the ion blocking layer comprises silicon oxide or silicon-aluminum oxide, the ion blocking layer is arranged between the second conductive layer and the second substrate, and the second electrode is arranged between the ion blocking layer and the second conductive layer.

Further, the electrochromic device further comprises an isolation layer, wherein the isolation layer is arranged between the ion blocking layer and the second substrate, and the isolation layer is at least one of titanium nitride, aluminum nitride, silicon nitride and boron nitride.

Further, a cathode coloring material is included in the electrochromic layer, and an anode coloring material is included in the ion storage layer.

Further, the cathode coloring material is at least one selected from tungsten oxynitride, molybdenum oxynitride, niobium oxynitride, titanium oxynitride and tantalum oxynitride, and the anode coloring material is at least one selected from nickel oxynitride, iridium oxynitride, manganese oxynitride, cobalt oxynitride, tungsten nickel oxynitride, tungsten iridium oxynitride, tungsten manganese oxynitride and tungsten cobalt oxynitride.

Further, the electrode assembly comprises a control module, wherein the control module is connected with the electrode and is positioned in the notch.

Further, the notch is filled with a conductive material, and the conductive material is electrically connected with the electrode.

Further, the conductive material is at least one selected from silver paste, carbon powder and copper paste.

Further, the wafer carrier comprises a cavity, wherein the cavity is positioned between the first substrate and the second substrate, and vacuum or inert gas filling is carried out in the cavity.

The invention has the technical effects that the product is highly integrated, a series of control or communication units can be additionally integrated, and the service life of the packaged glass product is prolonged.

The conception, specific structure, and technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, features, and effects of the present invention.

Drawings

Other features, objects and advantages of the present invention will become more apparent upon reading of the detailed description of non-limiting embodiments, made with reference to the accompanying drawings in which:

FIG. 1 is a schematic diagram of an embodiment of the present invention;

FIG. 2 is a schematic diagram of another embodiment of the present invention;

fig. 3 is a top view of an embodiment of the present invention.

The reference numerals illustrate 100-first substrate, 200-second substrate, 300-score, 400-wire, 501-first electrode, 502-second electrode, 600-dry body, 105-first conductive layer, 110-electrochromic stack, 115-second conductive layer, 120-ion blocking layer, 125-isolation layer, 130-cavity, 135-edge seal material.

Detailed Description

The following description of the preferred embodiments of the present invention refers to the accompanying drawings, which make the technical contents thereof more clear and easy to understand. The present invention may be embodied in many different forms of embodiments and the scope of the present invention is not limited to only the embodiments described herein.

In the drawings, like structural elements are referred to by like reference numerals and components having similar structure or function are referred to by like reference numerals. The dimensions and thickness of each component shown in the drawings are arbitrarily shown, and the present invention is not limited to the dimensions and thickness of each component. The thickness of the components is exaggerated in some places in the drawings for clarity of illustration.

As shown in fig. 1, the invention discloses electrochromic glass, which comprises a substrate, wherein the substrate comprises a first substrate 100 and a second substrate 200, an electrochromic device is arranged between the first substrate 100 and the second substrate 200, a first conductive layer 105, an electrochromic laminated layer 110 and a second conductive layer 115 are sequentially arranged from the first substrate 100, and the electrochromic laminated layer 110 comprises an electrochromic layer, an ion conducting layer and an ion storage layer. And an electrode configured to supply power to the electrochromic device, the change in current causing a fading effect to occur in the electrochromic device. The inner surface of the substrate includes a score groove 300, the score groove 300 being located opposite the electrode, the score groove 300 having a depth less than the thickness of the substrate, the periphery of the score groove 300 and the periphery of the substrate being sealed by the edge sealing material 135.

The substrate may be a planar glass. In one embodiment, the first transparent substrate 100 and the second transparent substrate 200 may also be curved glass.

The first conductive layer 105 and the second conductive layer 125 are conventional conductive layers, and the material includes one or more of Indium Tin Oxide (ITO), aluminum doped zinc oxide (AZO), boron doped zinc oxide (BZO), fluorine doped tin oxide (FTO).

Electrochromic stack 110 is a conventional electrochromic element that includes an electrochromic layer, an ion conducting layer, and an ion storage layer. In cooperation with the first conductive layer 105 and the second conductive layer 115 in the case of a forward voltage and a reverse voltage, can be reversibly switched in both a colored state and a bleached state, and has an overall resistance of about 2 to 10 ohms.

The bottom layer in the electrochromic layer stack 110is an electrochromic layer, and is disposed on the first conductive layer 105, and may be deposited on the first conductive layer 105 by vacuum coating, evaporation coating, or the like, with a film thickness of 200 to 600nm. The material is selected from one or more of tungsten oxide (WO ₃), molybdenum oxide (MoO ₃), niobium oxide (Nb ₂O₅) and titanium oxide (TiO ₂).

An ion conducting layer is then provided on the electrochromic layer for connecting ions between the electrochromic layer and the ion storage layer, the material preferably being metallic lithium, with a film thickness of 10 to 300nm. Materials such as tantalum, niobium, cobalt, aluminum, silicon, phosphorus, boron and the like can be doped in the lithium thin film layer in order to improve the stability of lithium ions and the ion void ratio to improve the transmission rate.

Finally, an ion storage layer is arranged on the ion conducting layer, and is used for storing lithium ions conducted from the electrochromic layer due to voltage effect, and the film thickness is 150-650 nm. The material of the ion storage layer is selected from one or more of nickel oxide (NiO _x) and iridium oxide (IrO ₂).

The electrode can be selected from conductive copper foil, copper-nickel welding strip, nickel-chromium welding strip, etc., and can form conductive narrow strips with high adhesion on the surface of the conductive film through the processes of vacuum coating, screen printing, dispensing, coating, etc., and then the electrode is connected with the first conductive layer 105 and the second conductive layer 125 through the modes of conductive adhesive bonding, laser welding, elastic pressing, etc.

The notch 300 is opposite to the electrode, and in actual use of the electrochromic glass, the electrodes on the first conductive layer 105 and the second conductive layer 115 need to be connected to each other by using a conductive wire to form a loop. At this time, additional conductive wires may be trimmed and stored in the score groove 300 nearby, hiding the conductive wires while achieving planarization of the electrochromic glass structure.

In addition, in some cases, the electrodes may be directly covered by the grooves 300 without using wires, and the electrodes may be directly extended beyond the first substrate 100 and the second substrate 200, and then the electrodes may be connected using conductive wires to form an energizing circuit.

The edge sealing material 135 is an all-inorganic or inorganic-metal slurry mixed material and can be selected from one or more of oxides of simple substances such as lithium, sodium, potassium, zinc, boron, aluminum, silicon, phosphorus, tin and bismuth. Preferred are lithium oxide (Li ₂ O), sodium oxide (Na ₂ O), potassium oxide (K ₂ O), zinc oxide (ZnO), boron oxide (B ₂O₃), aluminum oxide (Al ₂O₃), silicon dioxide (SiO ₂), phosphorus pentoxide (P ₂O₅), tin oxide (SnO), bismuth oxide (Bi ₂O₃).

Further, the notch 300 includes a drying body 600 for adsorbing moisture generated in the environment and between the substrates to improve the lifetime and reliability of the electrochromic glass, and preferably, the drying body 600 may be a molecular sieve, a silica gel, an activated alumina, or the like. Alternatively, there may be a plurality of grooves 300 on each substrate, each groove 300 is filled with a dry body, and in addition to the grooves 300 in which the conductive wires are placed, the extra grooves 300 may further absorb the surrounding moisture, further ensuring the lifetime of the electrochromic glass product.

Further, the electrodes include a first electrode 501 and a second electrode 502, the first electrode 501 is in electrical contact with the first conductive layer 105, the second electrode 502 is electrically connected with the second conductive layer 115, the first electrode 501 is located in a notch of the inner surface of the first substrate 100, and a width of the first electrode 501 corresponds to a width of the notch of the inner surface of the first substrate 100. Therefore, by adjusting the width of the notch 600 on the first substrate 100, the width of the first electrode 501 can be adjusted accordingly, so as to increase the contact area between the first electrode 501 and the first conductive layer 105, increase the current transmission rate, and reduce the resistance.

Further, the electrochromic device further includes an ion blocking layer 120, and the ion blocking layer 120 includes silicon oxide or silicon aluminum oxide. The ion blocking layer 120 is disposed between the second conductive layer 115 and the second substrate 200, over the second conductive layer 115. The ion blocking layer 120 uses silicon (Si) or silicon aluminum (SiAl) target material with a thickness of 20 to 80nm, and the components are silicon oxide (SiO _x), silicon aluminum oxide (SiAlO _x). Wherein, because the compactness of aluminum is good, the migration of sodium and magnesium in the glass can be effectively blocked, and the adhesion force of the electrochromic film on the glass is improved, so that the electrochromic film is not peeled off.

Further, the electrochromic device further includes an isolation layer 125, the isolation layer 125 being disposed between the ion blocking layer 120 and the second substrate 200. The thickness of the isolation layer 125 is 100 to 1000nm, and the material may be one or more of titanium nitride, aluminum nitride, silicon nitride, and boron nitride. The materials have higher transparency and higher resistance, can prevent current from escaping after the device is electrified, and can also protect each functional layer deposited below the materials, such as an electrochromic layer, an ion conducting layer and the like, so as to reduce the physical and chemical losses of the materials.

As shown in fig. 2, after the ion blocking layer 120 and the isolation layer 125 are introduced, the second electrode 502 maintains an electrical connection with the second conductive layer 115, and the ion blocking layer 120 and the isolation layer 125 cover the second electrode 502. The second electrode 502 is now contacted by the wire 400 through the score groove 300 of the second substrate 200. The wire 400 is stored in the notch 300 of the second substrate 200. At this time, the top view of the electrochromic glass is shown in fig. 3, that is, the grooves 300 are formed on two sides of the substrate, and the first electrode 501 or the second electrode 502 is led out from the grooves through a wire or directly according to different materials used, and then the normal operation can be started after the connection of the power supply. When the electrochromic glass is installed, the notch 300 can be blocked by the installation frame of the glass, and a user cannot observe the notch 300 when observing.

Further, a cavity 130 is also included, and the cavity 130 is located between the first substrate 100 and the second substrate 200, i.e., any portion other than the electrochromic device, or a portion of the electrochromic device not in contact with the encapsulation material 135 or the second substrate 200. The cavity 130 is either evacuated or filled with an inert gas. The inert gas can prevent the film layer of the electrochromic device from being oxidized, and the service life is influenced, namely the hollow electrochromic glass. And the vacuum is pumped in the electrochromic glass, so that the sound insulation performance of the electrochromic glass can be further enhanced besides protecting the film layer of the electrochromic device.

Electrochromic glasses can be reversibly cycled between a bleached state and a colored state when in use. In the bleached state, lithium ions are caused to pass through the ion conducting layer and into the electrochromic layer containing electrochromic material by applying a voltage at the first and second conductive layers 105, 115 to color them. When the voltage potentials applied at the first conductive layer 105 and the second conductive layer 115 are reversed, lithium ions leave the electrochromic layer and pass back into the ion storage layer through the ion conductive layer. Thereby, the device is switched to a bleached state. Depending on the voltage control, electrochromic glasses may not only switch back and forth between a bleached state and a colored state, but may also switch to one or more intermediate color states between the bleached state and the colored state.

Further, the electrochromic layer in electrochromic stack 110 includes a cathodic coloring material therein and the ion storage layer includes an anodic coloring material therein. For example, the electrochromic layer may employ a cathodic coloring material such as tungsten oxide and the ion storage layer may employ an anodic coloring material such as nickel oxide. That is, after lithium ions leave the ion storage layer, the ion storage layer also enters a colored state. Thus, the electrochromic layer and the ion storage layer combine and together reduce the amount of light transmitted through the stack.

Further, the electrochromic layer can be coated by using metal oxynitride deposition with a polycrystalline structure, the film thickness is usually 150 to 650 nanometers, the material used specifically comprises one or more of tungsten oxynitride (WO _xN_y), molybdenum oxynitride (MoO _xN_y), niobium oxynitride (NbO _xN_y), titanium oxynitride (TiO _xN_y) and tantalum oxynitride (TaO _xN_y), and the parameters of x and y correspondingly change according to the nitrogen content. The mole number of nitrogen atoms of the electrochromic layer 110 is generally 0.05% -20% of the mole number of the whole atoms, and may be 0.5% -5%, or may be 0.5% -10%. Generally, the nitrogen content exceeds 20%, the color of the deposited coating is deepened, which is caused by the color of the metal oxynitride, and the deepening of the coating color influences the light transmittance of the electrochromic glass in a fading state, so that the color changing range of a finished device is reduced.

After replacing the metal oxide used in the conventional electrochromic layer with metal oxynitride, according to the difference of nitrogen content, nitrogen ions replace oxygen ions in the original metal oxide, and tungsten is taken as an example, original W-O ionic bonds are partially replaced by W-N ionic bonds, so that the asymmetry of crystal lattices is caused, the acting force balance among the original ions is destroyed, adjacent atoms deviate from the balance position, and the crystal distortion is caused. After the crystal is distorted, interactions around the ion transport channel are reduced, thereby increasing the ion transport rate of the electrochromic layer. The nitrogen element is used as a relatively stable element, and the stability of the metal compound is not affected by the introduction of the nitrogen element, so that the nitrogen element still maintains good stability.

Similar to the electrochromic layer, the film thickness of the ion storage layer is 150-650 nm, the material is selected from one or more of nickel oxynitride (NiO _xN_y), iridium oxynitride (IrO _xN_y), manganese oxynitride (MnO _xN_y), cobalt oxynitride (CoO _xN_y), tungsten nickel oxynitride (WNi _zO_xN_y), tungsten iridium oxynitride (WIr _zO_xN_y), tungsten manganese oxynitride (WMn _zO_xN_y) and tungsten cobalt oxynitride (WCo _zO_xN_y), and the mole number of nitrogen atoms in the film layer accounts for about 0.05% -15% of the mole number of the whole atoms. Further incorporation of nitrogen into the conventional ion storage layer 120, from a conventional nickel oxide, iridium oxide material to a nickel oxynitride, iridium oxynitride or cobalt oxynitride material, may improve the stability of the device during the discoloration process due to the higher binding energy of the nitride relative to the oxide.

Further, the electrode assembly further comprises a control module, wherein the control module is connected with the electrode and is positioned in the notch 300. Because the control module is smaller and can be stored in the notch 300, the control module can further integrate a series of control or communication units such as wireless, photosensitive, sound control, laser and the like, thus integrating electrochromic glass and the control unit thereof, having simple and convenient operation and saving space, and realizing planarization and lightening of electrochromic glass products.

When the control module comprises a wireless unit, the electrochromic glass can be connected with a mobile phone, a computer, a tablet, a center console and the like in a wireless mode through Bluetooth or wifi and the control module, and then the color fading change of the electrochromic glass is controlled.

The voltage of the electrochromic glass passing through the electrochromic device can be automatically adjusted along with the light intensity by implanting the photosensitive element control module so as to control the transmittance of the electrochromic glass.

Further, a voice control unit can be additionally added to control the transmittance of the electrochromic through voice recognition AI.

Further, a laser module can be added, and laser conduction is adopted to remotely control the transmittance of the electrochromic glass at an ultra-long distance.

By adding the different control modules, the electrochromic glass can be widely applied to automobile skylights, side windows of motor cars, portholes of airplanes, portholes of ship loose wheels, intelligent curtain walls, intelligent household appliances and the like.

Further, the notch 300 is filled with a conductive material, and the conductive material is electrically connected to the electrode.

The conductive material can be mixed with the drying body 600, or the conductive material can be laid on the drying body 600 after the drying body 600 is laid on the notch 300, at this time, the electrode only needs to be in contact with the conductive material, or the electrode can be led out from the conductive material at the edge of the notch after being led out to the conductive material in the notch 300 through the lead 400, and the conductive wire is not required to be wound and placed in the notch 300, so that the space in the notch 300 is more regular.

Further, the conductive material may be at least one selected from silver paste, carbon powder, copper paste, for conducting current.

The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention without requiring creative effort by one of ordinary skill in the art. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.

Claims

1. An electrochromic glass, characterized in that it comprises a substrate, an electrochromic device, and an electrode, wherein the substrate comprises a first substrate and a second substrate, the electrochromic device is included between the first substrate and the second substrate, and the electrochromic device is sequentially provided with a first conductive layer, an electrochromic layer, an ion conduction layer, an ion storage layer, and a second conductive layer starting from the first substrate; the electrode is configured to supply power to the electrochromic device; the inner surface of the substrate comprises a groove, the groove is opposite to the electrode, the depth of the groove is less than the thickness of the substrate, the outer periphery of the groove and the periphery of the substrate are sealed by an edge sealing material; the groove comprises a dry body.

2. The electrochromic glass according to claim 1, characterized in that the drying body is one or more of molecular sieve, silica gel, and activated alumina.

3. The electrochromic glass as described in claim 1 is characterized in that the electrode includes a first electrode and a second electrode, the first electrode is electrically contacted with the first conductive layer, the second electrode is electrically connected to the second conductive layer, the first electrode is located in a groove on the inner surface of the first substrate, and the width of the first electrode corresponds to the width of the groove on the inner surface of the first substrate.

4. The electrochromic glass as described in claim 3 is characterized in that the electrochromic device also includes: an ion blocking layer; the ion blocking layer contains silicon oxide or silicon aluminum oxide, the ion blocking layer is arranged between the second conductive layer and the second substrate, and the second electrode is located between the ion blocking layer and the second conductive layer.

5. The electrochromic glass according to claim 4 is characterized in that the electrochromic device further comprises: an isolation layer; the isolation layer is arranged between the ion blocking layer and the second substrate, and the isolation layer is selected from at least one of the following materials: titanium nitride, aluminum nitride, silicon nitride, and boron nitride.

6 . The electrochromic glass according to claim 1 , wherein the electrochromic layer comprises a cathode coloring material, and the ion storage layer comprises an anode coloring material.

7. The electrochromic glass as described in claim 6 is characterized in that the cathode coloring material is selected from at least one of the following materials: tungsten oxynitride, molybdenum oxynitride, niobium oxynitride, titanium oxynitride, and tantalum oxynitride; the anode coloring material is selected from at least one of the following materials: nickel oxynitride, iridium oxynitride, manganese oxynitride, cobalt oxynitride, tungsten nickel oxynitride, iridium oxynitride, tungsten manganese oxynitride, and tungsten cobalt oxynitride.

8. The electrochromic glass according to claim 1, further comprising: a control module, wherein the control module is connected to the electrode and is located in the groove.

9. The electrochromic glass according to claim 1, characterized in that the grooves are filled with a conductive material, and the conductive material is electrically connected to the electrodes.

10 . The electrochromic glass according to claim 9 , wherein the conductive material is at least one selected from the following materials: silver paste, carbon powder, and copper paste.

11. The electrochromic glass according to claim 1, further comprising: a cavity, wherein the cavity is located between the first substrate and the second substrate, and the cavity is a vacuum or filled with an inert gas.