CN108279540B - Inorganic metal oxide ion storage layer, low-temperature solution processing method and application thereof - Google Patents
Inorganic metal oxide ion storage layer, low-temperature solution processing method and application thereof Download PDFInfo
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Abstract
The invention discloses an inorganic metal oxide ion storage layer, a low-temperature solution processing method and application thereof, belonging to the technical field of inorganic material preparation. The solution processing method of the inorganic metal oxide layer of the present invention comprises the steps of: 1) mixing precursor salt of inorganic metal oxide, a polar solvent and a ligand to obtain a precursor solution; 2) and forming a film by using the obtained precursor solution, carrying out heat treatment, and volatilizing the polar solvent to obtain the inorganic metal oxide layer. The metal film obtained by low-temperature post-treatment has high stability and high ion storage capacity under the condition of regulating and controlling the concentration and components of the precursor. The method does not need a complex high-temperature vacuum environment, and can prepare different types of metal oxide films with excellent performance at low temperature as ion storage layers by only using precursors of different oxides.
Description
Technical Field
The invention belongs to the technical field of inorganic material preparation, relates to an inorganic metal oxide layer, a preparation method and application thereof, and particularly relates to an inorganic metal oxide ion storage layer, a low-temperature solution processing method thereof and application thereof in an electrochromic device.
Background
The electrochromic device has wide application prospect in the fields of flexible display, intelligent windows, data storage and the like. Generally, an electrochromic device is composed of five layers, namely a transparent conductive layer (ITO), an electrochromic layer, an electrolyte layer, an ion storage layer, and a transparent conductive layer (ITO). Wherein the ion storage layer has a primary function of balancing ions shuttling between the electrolyte layer and the electrochromic layer. In an electrochromic device, the ion storage layer is critical. In most of the reported studies, the inorganic ion storage layer needs to be processed into a film by using a complicated method, such as a high temperature vacuum evaporation method, a sputtering coating, and the like. The sol-gel technology reported in recent years can prepare an ion storage layer by a solution processing method, so that the cost of the electrochromic device is greatly reduced. However, the sol-gel technology often requires high-temperature heat treatment, which increases energy consumption and limits the use of the method, and the high-temperature condition often causes the ion storage layer to generate cracks, thereby affecting the adhesion capability of the ion storage layer.
The existing processing methods of inorganic metal oxide ion storage layers all need complex processing procedures or high-temperature post-processing methods. In order to reduce the production cost of electrochromic devices, a low-temperature solution processing method of an inorganic ion storage layer is in urgent need.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide an inorganic metal oxide layer, a preparation method and a use thereof, and in particular, to an inorganic metal oxide ion storage layer, a low temperature solution processing method thereof and a use thereof in an electrochromic device. The solution processing method can prepare the metal oxide ion storage layer with excellent performance under the condition of low temperature, has high stability and high ion storage capacity, reduces the production cost and has wide application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method of solution processing an inorganic metal oxide layer, the method comprising the steps of:
(1) mixing precursor salt of inorganic metal oxide, a polar solvent and a ligand to obtain a precursor solution;
(2) and forming a film by using the obtained precursor solution, carrying out heat treatment, and volatilizing the polar solvent to obtain the inorganic metal oxide layer.
In the method, the specific polar solvent is adopted to realize the synergistic action of the precursor and the ligand of the inorganic metal oxide, and the stable inorganic metal oxide layer can be obtained through simple film formation and low-temperature heat treatment.
The following preferred technical solutions are not intended to limit the technical solutions provided by the present invention, and the technical objects and advantages of the present invention can be better achieved and achieved by the following preferred technical solutions.
In the present invention, the mixing order of the precursor of the inorganic metal oxide, the polar solvent and the ligand is not limited, and those skilled in the art can select them as needed. In order to better exert the synergistic effect of the polar solvent on the inorganic metal oxide and the ligand, the mixing in the step (1) is preferably performed in the following mixing sequence: firstly dissolving precursor salt of inorganic metal oxide in a polar solvent to obtain precursor salt solution, and then adding a ligand to obtain the precursor solution.
Preferably, the polar solvent includes any one or a combination of at least two of alcohols, ethers or ketones, preferably any one or a combination of at least two of isopropanol, ethanol or acetone, and more preferably a combination of isopropanol, ethanol and acetone.
In the present invention, the inorganic metal oxide layer may be a pure material layer or a doped inorganic metal oxide layer formed of at least two kinds of inorganic metal oxides.
Preferably, the inorganic metal oxide layer is an inorganic metal oxide ion storage layer, preferably including any one or a combination of at least two of a transition metal element or a group iii to group v element, and further preferably including any one or a combination of at least two of ceria, titania, vanadium oxide, chromium oxide, molybdenum oxide, nickel oxide, cobalt oxide, copper oxide, iron oxide, silver oxide, cadmium oxide, diini pentoxide, niobium oxide, tungsten trioxide, zinc oxide, or tricobalt tetraoxide. But not limited to the above-listed inorganic metal oxide ion storage layers, other inorganic metal oxide layers having good ion storage capacity commonly used in the art may also be used in the present invention.
As a preferred solution of the method of the present invention, for different kinds of metal oxides, their corresponding precursor salts have the following preferences to better adapt the low temperature solution processing method of the present invention and to obtain very high stability and ion storage capacity:
preferably, cerium oxide (CeO)2) The precursor salt of the ion storage layer is Ce (NH)4)2(NO3)6。
Preferably, titanium dioxide (TiO)2) The precursor salt of the ion storage layer is Ti (OCH (CH) 3)2)4And/or TiCl4。
Preferably molybdenum trioxide (MoO)3) Of ion storage layersThe precursor salt is Mo (OH)6。
Preferably, the precursor salt of the nickel monoxide (NiO) ion storage layer is Ni (NO)3)2·6H2O。
Preferably, Nie (Nb) pentoxide2O5) The precursor salt of the ion storage layer is NbCl5And/or Nb (OC)2H5)5。
Preferably, tungsten trioxide (WO)3) Precursor salt of ion storage layer is WCl6。
Preferably, the precursor salt of the zinc oxide (ZnO) ion storage layer is Zn (CH)3COO)2·2H2O。
Preferably, tricobalt tetraoxide (Co)3O4) The precursor salt of the ion storage layer is Co (NO)3)2·6H2O。
As a preferred embodiment of the method of the present invention, the concentration of the precursor salt solution obtained in step (1) is 0.01mol/L to 1mol/L, for example, 0.01mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.7mol/L, 0.8mol/L, or 1 mol/L.
Preferably, the mixing in step (1) is accompanied by ultrasound.
Preferably, the equipment used for ultrasound is an ultrasonic shatterer.
Preferably, the time of the ultrasound is 10min to 20min, such as 10min, 12min, 13min, 15min, 17min, 18min or 20min, etc., preferably 10 min.
Preferably, the ligand in step (2) includes any one of organic carboxylic acid, alcohol ether, amine or ester, preferably any one or a combination of at least two of acetic acid, ethylene glycol, glycol ether, citric acid, polyethylene glycol (such as polyethylene glycol 400), ethyl acetate, ethylenediamine tetraacetic acid or lactic acid.
In the present invention, the ligand may be used alone or in combination of a plurality of ligands.
More preferably, the ligand is an organic carboxylic acid, preferably any one of acetic acid, citric acid, ethylenediamine tetraacetic acid or lactic acid or a combination of at least two thereof. When the organic carboxylic acid ligand is adopted, the organic carboxylic acid ligand can be matched with a precursor salt solution obtained by dissolving in a polar solvent, so that the synergistic effect is better exerted, and the formation of the complete crystal form of the inorganic metal oxide is promoted.
Preferably, the concentration of the ligand in the precursor solution of step (1) is 0.001mol/L to 10mol/L, such as 0.001mol/L, 0.005mol/L, 0.01mol/L, 0.03mol/L, 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.5mol/L, 0.6mol/L, 0.8mol/L, 1mol/L, 1.5mol/L, 2.5mol/L, 3mol/L, 4mol/L, 4.5mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L or 10mol/L, etc., preferably 0.1mol/L to 1.0mol/L, so that the formed metal oxide has high ion storage capacity and electrochemical stability.
Preferably, the precursor solution in step (2) is a stable precursor solution, and the "stable precursor solution" refers to: the precursor solution did not agglomerate and did not precipitate when left under air for 6 months.
The precursor solution obtained in the step (2) can be directly used or mixed with ligand or other precursor liquid in a certain proportion and then applied to various solution processing methods.
Preferably, the film forming manner in the step (2) is: and coating the precursor solution on a substrate and drying to form a film with a certain thickness.
Preferably, the base is a conductive substrate.
Preferably, the coating is a solution coating method, preferably including any one of spin coating, blade coating, wire bar coating, extrusion coating, gravure coating, dimple coating, or screen coating.
Preferably, the coating is spin coating, the spin coating speed is preferably 800rpm to 6000rpm, such as 800rpm, 900rpm, 1000rpm, 1100rpm, 1150rpm, 1200rpm, 1300rpm, 1400rpm, 1500rpm, 1750rpm, 2000rpm, 2200rpm, 2350rpm, 2500rpm, 2700rpm, 3000rpm, 3500rpm, 3800rpm, 4200rpm, 4600rpm, 5000rpm, 5500rpm or 6000rpm, and the like, and more preferably 1000 rpm.
The heat treatment of the present invention is a low temperature heat treatment, and the temperature of the heat treatment is 80 to 140 ℃, for example, 80 ℃, 85 ℃, 90 ℃, 92 ℃, 95 ℃, 97 ℃, 100 ℃, 120 ℃ or 140 ℃, and the like, preferably 120 ℃.
As a further preferred technical solution of the method of the present invention, the method comprises the steps of:
(1) dissolving precursor salt of inorganic metal oxide in a polar solvent, and treating for 10min by using an ultrasonic shattering machine to obtain precursor salt solution with the concentration of 0.01-1.0M;
then adding a ligand into the precursor salt solution to obtain a stable precursor solution, wherein the concentration of the ligand in the stable precursor solution is 0.001-10 mol/L;
(2) coating the stable precursor solution on a conductive substrate by a solution coating method, performing heat treatment at 80-140 ℃, and volatilizing a polar solvent to obtain an inorganic metal oxide layer;
wherein, the polar solvent is any one of isopropanol, ethanol or acetone or the combination of at least two of the isopropanol, the ethanol and the acetone.
In a second aspect, the present invention provides an inorganic metal oxide layer prepared by the method of the first aspect, the inorganic metal oxide layer being an inorganic metal oxide ion storage layer, preferably including any one or a combination of at least two of a transition metal element or a group iii to group v element, and further preferably including any one or a combination of at least two of ceria, titania, vanadium oxide, chromium oxide, molybdenum oxide, nickel oxide, cobalt oxide, copper oxide, iron oxide, silver oxide, cadmium oxide, diini pentoxide, niobium oxide, tungsten trioxide, zinc oxide, or tricobalt tetraoxide.
Preferably, the inorganic metal oxide layer has a thickness of 10nm to 10 μm, for example 10nm, 20nm, 35nm, 50nm, 65nm, 80nm, 100nm, 200nm, 300nm, 400nm, 600nm, 800nm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 10 μm or the like.
In a third aspect, the present invention provides an electrochromic device comprising a conductive layer, an electrochromic layer, an electrolyte layer, and the inorganic metal oxide layer of claim 9 as an ion storage layer;
preferably, the electrochromic device comprises a transparent conducting layer, an electrochromic layer, an electrolyte layer, an ion storage layer which is the inorganic metal oxide layer in the third aspect, and a transparent conducting layer from bottom to top.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention realizes the synergistic effect of the precursor of the inorganic metal oxide and the ligand by adopting a specific polar solvent, and obtains a plurality of high-efficiency ion storage layers of the electrochromic device through simple solution coating film formation and low-temperature heat treatment. Compared with the method for preparing the metal oxide in the literature, the formed metal oxide film does not need to be fired at the temperature higher than 200 ℃, only needs low-temperature post-treatment below 150 ℃, and the product also has excellent ion storage layer capacity, so that the production cost of the ion storage layer of the electrochromic device is greatly reduced under the condition of ensuring the precursor of the product quality.
(2) The invention proves that the metal film obtained by low-temperature post-treatment has high stability and high ion storage capacity under the condition of regulating and controlling the concentration and the components of the precursor. Compared with the traditional method, the method of the invention does not need a complex high-temperature vacuum environment, and can prepare different types of metal oxide films with excellent performance at low temperature as ion storage layers by only using precursors of different oxides.
Drawings
Fig. 1 is a cyclic voltammogram of the titanium oxide ion storage layer in example 1.
FIG. 2 is a cyclic voltammogram of the molybdenum oxide ion storage layer in example 2; the molybdenum trioxide precursor is used for rotary coating at the rotating speed of 1000rpm to form a film.
FIG. 3 is a cyclic voltammogram of the ion storage layer of titanium oxide 1:1 doped cerium oxide in example 4.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
Example 1
TiO2Preparation of ion storage layer
The vial was charged with 2 mL of isopropanol solution, and 0.66 mL of Ti (OCH (CH) was added3)2)4. In an ultrasonic sample jar crusher, sonicated for 10 minutes, 100 microliters of acetic acid was added as a ligand. The prepared solution can be directly processed into TiO on the surface of indium tin oxide by using a solution spin coating method at the rotating speed of 1000rpm 2A film. The film was placed in a 100 ℃ oven for heat treatment for ten minutes to remove the isopropanol solvent.
FIG. 1 is a cyclic voltammogram of the titanium oxide ion storage layer in example 1, and it can be seen from the cyclic voltammogram that the prepared titanium oxide film has high ion storage capacity and good electrochemical reversibility.
Example 2
MoO3Preparation of ion storage layer
A vial was charged with 2 mL of isopropanol solution, followed by 100. mu.L of acetic acid and 0.66 mL of MoCl3. Sonicate for 10 minutes in a sonicator jar. The prepared solution can be directly processed into MoO on the surface of indium tin oxide by using a solution spin coating method at the rotating speed of 1000rpm3A film. The film was placed in a 120 ℃ oven for heat treatment for ten minutes to remove the isopropanol solvent.
FIG. 2 is a cyclic voltammogram of the molybdenum oxide ion storage layer in example 2, and it can be seen from the cyclic voltammogram that the prepared molybdenum oxide film has high ion storage capacity and good electrochemical reversibility.
Example 3
TiO2Doped MoO3Preparation of ion storage layer
A vial was charged with 2 mL of isopropanol solution and 10. mu.L of acetic acid, followed by 0.66 mL of MoCl3. Mixing Ti (OCH (CH)3)2)4Adding into MoCl3 solution according to a certain proportion to prepare TiO2Doped MoO3And (3) solution. For example, the molar ratio of Mo to Ti is 2:1, the molar ratio of Mo to Ti is 3:1, and the molar ratio of Mo to Ti is 10: 1. The prepared solution can be directly processed into TiO on the surface of indium tin oxide by using a solution spin coating method at the rotating speed of 1000rpm 2Doped MoO3A film. The film was placed in a 120 ℃ oven for heat treatment for ten minutes to remove the isopropanol solvent.
Example 4
TiO2Doped CeO2Preparation of ion storage layer
A vial was charged with 2 ml of isopropanol solution and 10. mu.L of citric acid, and then 0.66 ml of Ce (NH)4)2(NO3)6. Mixing Ti (OCH (CH)3)2)4Adding into Ce (NH) according to a certain proportion4)2(NO3)6In solution, TiO can be prepared2Doped CeO2And (3) solution. If the molar ratio of Ti to Ce is 1:1, the molar ratio of Ti to Ce is 2:1, the molar ratio of Ti to Ce is 3:1 and the molar ratio of Ti to Ce is 10:1, the prepared solution can be directly processed into TiO on the surface of indium tin oxide by using a solution spin coating method at the rotating speed of 1000rpm2Doped CeO2A film. The film was placed in a 100 ℃ oven for heat treatment for ten minutes to remove the isopropanol solvent.
FIG. 3 is a cyclic voltammogram of the ion storage layer of example 4 in which the titanium oxide is doped with cerium oxide at a ratio of 1:1, and it can be seen that the titanium oxide ion storage layer has good ion storage capacity.
Example 5
Nb2O5Preparation of ion storage layer
The vial was charged with 20 ml of ethanol solution, 3. mu.l of acetic acid and 1 ml of Nb (OC)2H5)5. Sonicate for 15 minutes in a sonicator jar. The prepared solution can be directly processed into MoO on the surface of indium tin oxide by using a solution spin coating method at the rotating speed of 1500rpm 3A film. The film was placed in an oven at 140 ℃ for a heat treatment of ten minutes to remove the ethanol solvent.
Comparative example 1
The preparation method and conditions were the same as in example 1 except that the polar solvent was replaced with the nonpolar solvent.
The precursor solution phase separated after mixing and gradually precipitated. After half an hour, the solution completely precipitated.
The applicant states that the present invention is illustrated by the above examples to show the detailed method of the present invention, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be carried out. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (40)
1. A method of solution processing an inorganic metal oxide layer, the method comprising the steps of:
(1) mixing precursor salt of inorganic metal oxide, a polar solvent and a ligand to obtain a precursor solution; the polar solvent comprises any one or the combination of at least two of alcohols, ethers or ketones, precursor salt of the inorganic metal oxide and the polar solvent form precursor salt solution, and the concentration of the precursor salt solution is 0.01M-1.0M; the precursor solution is stable;
(2) Forming a film by using the obtained precursor solution, carrying out heat treatment, and volatilizing a polar solvent to obtain an inorganic metal oxide layer serving as an ion storage layer; the temperature of the heat treatment is 80-140 ℃; the film forming method comprises the following steps: and coating the obtained precursor solution on a substrate to form a film.
2. The method of claim 1, wherein the mixing of step (1) is: firstly, dissolving precursor salt of inorganic metal oxide in a polar solvent to obtain precursor salt solution, and then adding a ligand to obtain the precursor solution.
3. The method according to claim 1, wherein the polar solvent is any one of isopropyl alcohol, ethanol or acetone or a combination of at least two thereof.
4. The method of claim 3, wherein the polar solvent is a combination of isopropanol, ethanol, and acetone.
5. The method of claim 1, wherein the inorganic metal oxide layer is a pure material layer or a doped inorganic metal oxide layer formed of at least two inorganic metal oxides.
6. The method of claim 1, wherein the inorganic metal oxide layer is an inorganic metal oxide ion storage layer.
7. The method of claim 6, wherein the inorganic metal oxide layer comprises a transition metal element or any one of a third subgroup to a fifth subgroup element or a combination of at least two thereof.
8. The method of claim 7, wherein the inorganic metal oxide layer comprises any one of or a combination of at least two of ceria, titania, vanadia, chromia, molybdenum oxide, nickel oxide, cobalt oxide, copper oxide, iron oxide, silver oxide, cadmium oxide, diini pentoxide, niobium oxide, tungsten trioxide, zinc oxide, or tricobalt tetraoxide.
9. The method of claim 1, wherein the precursor salt of the ceria ion storage layer is Ce (NH)4)2(NO3)6。
10. The method of claim 1, wherein the precursor salt of the titanium dioxide ion storage layer is Ti (OCH (CH)3)2)4And/or TiCl4。
11. The method according to claim 1, wherein the precursor salt of the molybdenum trioxide ion storage layer is Mo (OH)6。
12. According to the claimThe method according to claim 1, wherein the precursor salt of the nickel monoxide ion storage layer is Ni (NO)3)2·6H2O。
13. The method of claim 1, wherein the precursor salt of the ion storage layer is NbCl 5And/or Nb (OC)2H5)5。
14. The method as claimed in claim 1, wherein the precursor salt of the tungsten trioxide ion storage layer is WCl6。
15. The method of claim 1, wherein the precursor salt of the zinc oxide ion storage layer is Zn (CH)3COO)2·2H2O。
16. The method according to claim 1, wherein the precursor salt of the tricobalt tetraoxide ion storage layer is Co (NO)3)2·6H2O。
17. The method of claim 1, wherein the mixing of step (1) is accompanied by ultrasound.
18. The method of claim 17, wherein the equipment used for ultrasound is an ultrasonic jar.
19. The method of claim 17, wherein the sonication time is between 10min and 20 min.
20. The method of claim 19, wherein the sonication time is 10 min.
21. The method according to claim 1, wherein the ligand in step (2) comprises any one of organic carboxylic acids, alcohols, alcohol ethers, amines or esters.
22. The method of claim 21, wherein the ligand in step (2) is any one of acetic acid, ethylene glycol, glycol ether, citric acid, polyethylene glycol, ethyl acetate, ethylenediamine tetraacetic acid or lactic acid or a combination of at least two of them.
23. The method of claim 21, wherein the ligand is an organic carboxylic acid.
24. The method of claim 21, wherein the ligand is any one of acetic acid, citric acid, ethylenediaminetetraacetic acid, or lactic acid, or a combination of at least two thereof.
25. The method according to claim 1, wherein the concentration of the ligand in the precursor solution in the step (2) is 0.001mol/L to 10 mol/L.
26. The method of claim 25, wherein the concentration of the ligand in the precursor solution of step (2) is 0.1mol/L to 1 mol/L.
27. The method of claim 1, wherein the base is a conductive substrate.
28. The method of claim 1, wherein the coating is a solution coating process.
29. The method of claim 1, wherein the coating comprises any one of spin coating, blade coating, wire bar coating, extrusion coating, gravure coating, dimpled coating, or screen coating.
30. The method of claim 29, wherein the coating is spin coating.
31. The method of claim 30, wherein the spin coating is performed at a speed of 800rpm to 6000 rpm.
32. The method of claim 31, wherein the spin coating is performed at 1000 rpm.
33. The method of claim 1, wherein the temperature of the heat treatment is 120 ℃.
34. Method according to claim 1, characterized in that it comprises the following steps:
(1) dissolving precursor salt of inorganic metal oxide in a polar solvent, and treating for 10min by using an ultrasonic shattering machine to obtain precursor salt solution with the concentration of 0.01-1.0 mol/L;
then adding a ligand into the precursor salt solution to obtain a stable precursor solution, wherein the concentration of the ligand in the stable precursor solution is 0.001-10 mol/L;
(2) coating the stable precursor solution on a conductive substrate by a solution coating method, performing heat treatment at 80-140 ℃, and volatilizing a polar solvent to obtain an inorganic metal oxide layer;
wherein, the polar solvent is any one of isopropanol, ethanol or acetone or the combination of at least two of the isopropanol, the ethanol and the acetone.
35. An inorganic metal oxide layer prepared according to any of claims 1 to 34, wherein the inorganic metal oxide layer is an inorganic metal oxide ion storage layer.
36. The inorganic metal oxide layer of claim 35, wherein the inorganic metal oxide layer comprises a transition metal element or any one of a third subgroup to a fifth subgroup element or a combination of at least two thereof.
37. The inorganic metal oxide layer of claim 36, wherein the inorganic metal oxide layer comprises any one of or a combination of at least two of ceria, titania, vanadia, chromia, molybdenum oxide, nickel oxide, cobalt oxide, copper oxide, iron oxide, silver oxide, cadmium oxide, diini pentoxide, niobium oxide, tungsten trioxide, zinc oxide, or tricobalt tetraoxide.
38. The inorganic metal oxide layer of claim 35, wherein the inorganic metal oxide layer has a thickness of 10nm to 10 μm.
39. An electrochromic device comprising a conductive layer, an electrochromic layer, an electrolyte layer and an inorganic metal oxide layer according to any one of claims 35 to 38 as an ion storage layer.
40. The electrochromic device according to claim 39, wherein said electrochromic device comprises a transparent conductive layer, an electrochromic layer, an electrolyte layer, an ion storage layer comprising an inorganic metal oxide layer according to any one of claims 35 to 38, and a transparent conductive layer from bottom to top.
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| CN103613136B (en) * | 2013-11-21 | 2015-09-16 | 镇江市高等专科学校 | A kind of preparation method of square MoO3 nanosheet |
| US10061177B2 (en) * | 2014-07-23 | 2018-08-28 | Kinestral Technologies, Inc. | Process for preparing multi-layer electrochromic stacks |
| CN107359255B (en) * | 2016-12-22 | 2019-08-09 | 广东聚华印刷显示技术有限公司 | Organic electroluminescence device and preparation method thereof |
| CN107561809A (en) * | 2017-09-18 | 2018-01-09 | 北京工业大学 | Towards the WO of automobile adhesive film3The preparation method of electrochromic device |
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