CN117343489A - Composition for preparing patterned electrochromic device and application - Google Patents
Composition for preparing patterned electrochromic device and application Download PDFInfo
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- CN117343489A CN117343489A CN202310818350.8A CN202310818350A CN117343489A CN 117343489 A CN117343489 A CN 117343489A CN 202310818350 A CN202310818350 A CN 202310818350A CN 117343489 A CN117343489 A CN 117343489A
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- 239000000203 mixture Substances 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 14
- -1 poly (3, 3-bis ((2-ethylhexyl) oxy) methyl) -6, 8-dimethyl-3, 4-dihydro-2H-thieno [3,4-b ] [1,4] dioxaepine Chemical compound 0.000 claims abstract description 13
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 239000011245 gel electrolyte Substances 0.000 claims description 20
- 239000000758 substrate Substances 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- 239000002608 ionic liquid Substances 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 4
- PXKPKGHXANCVMC-UHFFFAOYSA-N 3-butyl-1-methyl-1,2-dihydroimidazol-1-ium;trifluoromethanesulfonate Chemical compound OS(=O)(=O)C(F)(F)F.CCCCN1CN(C)C=C1 PXKPKGHXANCVMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims description 2
- 238000000265 homogenisation Methods 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004417 polycarbonate Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000003446 memory effect Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
- G02F1/1514—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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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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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- 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
- G02F1/1516—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 organic 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
- G02F1/153—Constructional details
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
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- C09K2211/145—Heterocyclic containing oxygen as the only heteroatom
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
- C09K2211/1441—Heterocyclic
- C09K2211/1458—Heterocyclic containing sulfur as the only heteroatom
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- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention discloses a composition for preparing a patterned electrochromic device and application thereof, wherein the composition consists of an electrochromic material, a photo-crosslinking agent and a solvent; the electrochromic material is poly (3, 3-bis ((2-ethylhexyl) oxy) methyl) -6, 8-dimethyl-3, 4-dihydro-2H-thieno [3,4-b ] [1,4] dioxaepine; the photocrosslinker is biaziridine photocrosslinker 2CNN. According to the invention, the photo-crosslinking agent is added into the electrochromic material, so that the prepared electrochromic film can achieve the photo-crosslinking effect under the irradiation of 365nm ultraviolet light by using different photomasks, and different patterned electrochromic films can be prepared by using different photomasks. The symmetrical patterned electrochromic device prepared by the method has good bistable property, extremely low driving voltage and can control the pattern switching of the patterned electrochromic device through wireless equipment.
Description
Field of the art
The invention relates to a composition for preparing a patterned electrochromic device and application thereof.
(II) background art
Electrochromic polymer (ECP) display devices are typical non-radiative (passive) display devices, and their power consumption is several tens of times that of common LCD display screens due to their extremely low driving voltages, and are considered as new generation display devices, but the application of electrochromic devices is greatly limited due to the inability to realize the preparation of fine patterned electrochromic films.
The biaziridine photocrosslinker reacts with the solubilised alkyl chain of the polymer in a short time under the irradiation of ultraviolet light to obtain the conductive polymer with a crosslinked structure and obviously reduced solubility. If only specific areas of the polymers are cross-linked to each other during the photo-crosslinking process, patterning is substantially completed, and thus, screening of suitable electrochromic polymers and cross-linking agents is required, and it is desirable to produce high precision patterned electrochromic devices.
(III) summary of the invention
The invention aims to provide a composition for preparing a patterned electrochromic device and application thereof, wherein different patterned electrochromic films are prepared by using a soluble electrochromic material P (ProDot) (Pm) and a biaziridine photocrosslinker and different photomasks, and a patterned electrochromic display device is constructed by using the composition; the electrochromic display device is extremely low in required driving voltage, can be driven by using primary batteries such as a solar panel and a cola battery with the voltage of 1.5V, and can be controlled by using a novel EC control module in a wireless manner to adjust the display content of the device. Solves the problem that the conventional common equipment cannot prepare high-precision electrochromic patterns.
The technical scheme adopted by the invention is as follows:
the invention provides a composition for preparing a patterned electrochromic device, which consists of an electrochromic material, a photocrosslinker and a solvent;
the electrochromic material is poly (3, 3-bis ((2-ethylhexyl) oxy) methyl) -6, 8-dimethyl-3, 4-dihydro-2H-thieno [3,4-b ] [1,4] dioxalever) (P (Prodot) for short, polymerization degree 28000-30000), synthesized according to Macromolecules 2004,37,20,7559-7569, is magenta in normal state or neutral state, and becomes colorless when a positive voltage is applied;
the photocrosslinker is biaziridine photocrosslinker 2CNN, synthesized according to documents Angewandte Chemie,2021,133 (39): 21691-21698;
preferably, the mass ratio of the photocrosslinker to the electrochromic material is 1:1-3; the volume dosage of the solvent is 0.1-0.3 mL/mg based on the mass of the electrochromic material.
Preferably, the solvent is dichloromethane or chloroform.
The invention also provides application of the composition in preparing a symmetrical patterned electrochromic device, wherein the structure of the symmetrical patterned electrochromic device sequentially comprises a first ITO substrate, a first patterned electrochromic layer, a gel electrolyte layer, a second patterned electrochromic layer and a second ITO substrate, and the symmetrical patterned electrochromic device is prepared according to the following method: (1) Under the condition of avoiding light, dissolving an electrochromic material and a photo-crosslinking agent in a solvent, uniformly mixing by ultrasonic, spraying a film on the conductive surface of ITO glass by using a spray gun, and marking as a first ITO substrate-first electrochromic film; preparing a second ITO substrate-a second electrochromic film by the same method; (2) Covering the surfaces of the electrochromic films of the first ITO substrate-first electrochromic film and the second ITO substrate-second electrochromic film prepared in the step (1) with a photomask, carrying out photocrosslinking under 365nm ultraviolet irradiation, and removing uncrosslinked parts by using dichloromethane to prepare a patterned electrochromic film, namely a first ITO substrate-first patterned electrochromic film and a second ITO substrate-second patterned electrochromic film; (3) And (3) adhering the peripheries of the first ITO substrate-first patterned electrochromic film, the first patterned electrochromic film layer of the second ITO substrate-second patterned electrochromic film and the second patterned electrochromic film layer by using 3M glue, forming a cavity in the middle, adding a proper amount of gel electrolyte into the cavity to form a gel electrolyte layer, dipping ethanol and dichloromethane in sequence, wiping by using cotton to remove redundant gel electrolyte, and then placing in a 60 ℃ oven for 3h to obtain the symmetrical patterned electrochromic device.
Preferably, the mass ratio of the photocrosslinker to the electrochromic material in the step (1) is 1:1-3; the volume dosage of the solvent is 0.1-0.3 mL/mg based on the mass of the electrochromic material.
Preferably, the ultrasonic mixing in the step (1) is ultrasonic in an ultrasonic machine at 50kHz for 10min.
Preferably, the photocrosslinking in step (2) is carried out at 1000mW/cm 2 Is photocrosslinked for 90s under 365nm ultraviolet light irradiation.
Preferably, the photomask in the step (2) comprises a two-dimensional code pattern.
Preferably, the gel electrolyte of step (3) is prepared as follows: swelling polymethyl methacrylate (PMMA, molecular weight of 800000 g/mol) and polypropylene carbonate (PC, molecular weight of 102.09) in oven at 60deg.C for 7 days to obtain substrate, adding LiBF 4 And acetonitrile and dichloromethane solution of ionic liquid, and spin-evaporating to remove solvent after uniform mixing to obtain gel electrolyte. The added mass of PMMA is 0.28-0.32 g/mL based on the volume of PC; the LiBF 4 The added mass of the catalyst is 0.04-0.041 g/mL based on the volume of PC; the ionic liquid is 1-n-butyl-3-methylimidazole trifluoromethane sulfonate; the added mass of the ionic liquid is 0.22-0.23 g/mL based on the volume of PC; the volume ratio of acetonitrile to dichloromethane is 1:1, a step of; the total volume of acetonitrile and dichloromethane is 0.4-0.6ml/ml calculated by the volume of PC.
The invention also provides a symmetrical patterned electrochromic device prepared by using the composition, and the symmetrical patterned electrochromic device structure sequentially comprises a first ITO substrate, a first patterned electrochromic layer, a gel electrolyte layer, a second patterned electrochromic layer and a second ITO substrate.
The symmetrical patterned electrochromic device prepared by the method can be used for manufacturing electrochromic two-dimensional code payment devices.
Compared with the prior art, the invention has the beneficial effects that:
according to the composition for preparing the patterned electrochromic device, the photo-crosslinking agent is introduced into the electrochromic field for the first time, and as the bisaziridine photo-crosslinking agent generates carbene after being irradiated by 365nm ultraviolet light, insertion reaction is easy to occur between the bisaziridine photo-crosslinking agent and methine in an alkyl side chain of a soluble electrochromic material, so that the originally soluble electrochromic material is converted into insoluble electrochromic material. By adding the photo-crosslinking agent into the electrochromic material, the prepared photochromic film can achieve the photo-crosslinking effect with different photomasks under 365nm ultraviolet irradiation, so that different patterned electrochromic films can be prepared by using different photomasks. The symmetrical patterned electrochromic device prepared by the method is a superposition of two patterns (such as two-dimensional codes) when no voltage is applied, has a good hiding function, can display the pattern (the two-dimensional codes) A or B when +/-0.4V is applied, has good bistable property, can still keep an identifiable state for 24 hours after the voltage is removed, and can clearly read the pattern (the two-dimensional codes) after the device circulates for 30 ten thousands times, so that the practical requirement is completely met. In addition, because the driving voltage of the device is extremely low, the device can be driven by taking primary batteries such as a 1.5V solar panel, a cola battery, a lemon battery, a brine battery and the like as external power sources. In addition, when the EC control module is externally connected, the positive and negative of the voltage can be controlled wirelessly to adjust the display content of the device, and the pattern switching of the patterned electrochromic device can be controlled through wireless equipment.
(IV) description of the drawings
Fig. 1, schematic diagram of a process for fabricating a symmetric patterned electrochromic device.
Fig. 2, photograph of patterned electrochromic film prepared in example 1.
Fig. 3, photograph of electrochromic pattern based on Pc.
Fig. 4, py-based electrochromic pattern photographs.
Fig. 5 is a schematic diagram of a memory effect of a symmetric two-dimensional code patterned electrochromic device.
Fig. 6, cyclic test of symmetric two-dimensional code patterned electrochromic device.
Fig. 7, photographs of different driving power driven symmetric patterned electrochromic devices.
Fig. 8 is a schematic diagram of controlling pattern switching of a symmetric two-dimensional code patterned electrochromic device by a wireless device.
(fifth) detailed description of the invention
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
the poly (4, 7-bis (3, 3-bis ((2-ethylhexyl) oxy) methyl) -8-methyl-3, 4-dihydro-2H-thieno [3,4-b ] [1,4] dioxan-6-yl) benzo [ c ] [1,2,5] thiadiazole) (hereinafter abbreviated to Pc) of the examples of the present invention were prepared according to patent CN 111393616A; poly (3- (3, 3-bis ((2-ethylhexyl) oxy) methyl) -8-methyl-3, 4-dihydro-2H-thieno [3,4-b ] [1,4] dioxapan-6-yl) -1-dodecyl-10-methyl-1H-phenanthrene [1, 10,9,8-cdefg ] carbazole) (hereinafter Py) prepared according to patent CN 111393616A; poly (3, 3-bis ((2-ethylhexyl) oxy) methyl) -6, 8-dimethyl-3, 4-dihydro-2H-thieno [3,4-b ] [1,4] dioxapine) (abbreviated as P (Prodot), polymerization degree 28000-30000) is synthesized according to Macromolecules 2004,37,20,7559-7569, and a normal state or a neutral state is magenta, and a positive voltage is applied to the mixture to turn the mixture colorless.
The gel electrolyte is prepared as follows: 6g of polymethyl methacrylate (PMMA, molecular weight 800000 g/mol) and 20mL of polycarbonate (PC, molecular weight 102.09) were swelled in an oven at 60℃for 7 days to prepare a substrate, and 0.81g of LiBF dissolved in 4 And 4.44g of an ionic liquid (1-n-butyl-3-methylimidazole trifluoromethane sulfonate) in 5ml of acetonitrile and 5ml of methylene chloride were uniformly mixed, and the solvent was removed by rotary evaporation to prepare a gel electrolyte.
Example 1, symmetrical two-dimensional code electrochromic device
Adopting the flow shown in fig. 1, the symmetrical two-dimensional code electrochromic device is prepared according to the following steps, and the structure sequentially comprises a first ITO substrate, a first two-dimensional code electrochromic layer, a gel electrolyte layer, a second two-dimensional code electrochromic layer and a second ITO substrate:
(1) Spraying of electrochromic films:
under the condition of avoiding light, 10mg of P (Prodot) and 4mg of photo-crosslinking agent 2CNN are dissolved in 2mL of dichloromethane, ultrasonic is carried out for 10min in a 50kHz ultrasonic machine, and a film with the thickness of about 100nm is sprayed on a conductive surface of ITO glass with the thickness of 25 x 40cm by using a spray gun, so that a first ITO substrate-first electrochromic film layer is formed.
The same method is used for preparing a second ITO substrate-a second electrochromic film layer.
(2) Preparing a two-dimensional code electrochromic film:
respectively covering the two-dimensional code mask plates on the surfaces of the electrochromic film layers of the first ITO substrate, the first electrochromic film layer and the second ITO substrate, the second electrochromic film layer, wherein the intensity of the two-dimensional code mask plates is 1000mW/cm 2 After the ultraviolet irradiation of 365nm is finished, dichloromethane is used for washing to wash out uncrosslinked parts, so that the two-dimensional code electrochromic film is prepared, and a first ITO substrate-first two-dimensional code electrochromic film layer and a second ITO substrate-second two-dimensional code electrochromic film layer are respectively obtained.
(3) Preparation of a symmetrical two-dimensional code electrochromic device:
and (3) adhering the peripheries of the first ITO substrate-first two-dimensional code electrochromic film layer, the second ITO substrate-second two-dimensional code electrochromic film layer and the first two-dimensional code electrochromic film layer by using 3M glue to form a cavity, adding a proper amount of gel electrolyte into the cavity to form a gel electrolyte layer, dipping in ethanol and dichloromethane sequentially to wipe out excessive gel electrolyte, and then placing in a 60 ℃ oven to dry for 10 hours to obtain the symmetrical two-dimensional code patterned electrochromic device, as shown in figure 1.
Comparative example 1 preparation of electrochromic patterns based on Pc
Under the condition of light shielding, 5mg of Pc and 2mg of photo-crosslinking agent 2CNN are dissolved in 1mL of chloroform, the mixture is subjected to ultrasonic treatment in a 50kHz ultrasonic machine for 3min, and a film with the thickness of about 100nm is sprayed on the conductive surface of ITO glass with the thickness of 25 cm by using a spray gun, namelyCovering the surface of the electrochromic film layer with a lattice mask at an intensity of 1000mW/cm 2 After completion of photocrosslinking for 150s under 365nm ultraviolet light irradiation, the uncrosslinked portions were washed off by rinsing with methylene chloride to prepare an electrochromic pattern based on Pc. As shown in fig. 3, a part of the electrochromic pattern based on Pc was obviously not crosslinked completely, proving that the biaziridine photocrosslinker had poor crosslinking effect for Pc.
Comparative example 2 preparation of Py-based electrochromic patterns
Under the condition of avoiding light, 5mg of Py and 2mg of photo-crosslinking agent 2CNN are dissolved in 1mL of chloroform, ultrasonic treatment is carried out for 3min in a 50kHz ultrasonic machine, a film with the thickness of about 100nm is sprayed on the conductive surface of ITO glass with the thickness of 25 mm and 40cm by using a spray gun, namely an electrochromic film layer, a rabbit mask is covered on the surface of the electrochromic film layer, and the intensity is 1000mW/cm 2 After completion of photocrosslinking for 150s under 365nm ultraviolet light irradiation, the uncrosslinked portions were washed off by rinsing with methylene chloride to prepare a Py-based electrochromic pattern. As shown in fig. 4, a portion of the Py-based electrochromic pattern was visibly not fully crosslinked and the electrochromic pattern of the polymer was visually insignificant and unsuitable for preparing patterned electrochromic films.
Example 2 Performance test of symmetric two-dimensional code electrochromic device
1. Memory effect test
Applying +/-0.4V voltage to two ends of the symmetrical two-dimensional code electrochromic device prepared in the embodiment 1 by using a Chenhua 660 electrochemical workstation, removing the external voltage after 5s, standing for different times (0 min, 15min, 30min, 45min, 1h, 3h, 5h, 18h and 24 h) at room temperature, shooting by using a camera, and finding that the two-dimensional code electrochromic device can be still identified after removing the external voltage for 24h as shown in a result of fig. 5.
2. Cycle test
The symmetrical two-dimensional code electrochromic device prepared in the embodiment 1 is continuously applied with a step voltage of +/-0.4V at two ends by using a Kai KV-EC-7500 electrochromic device circulation tester, the step time is 3s, the cycle is 30 ten thousand times, the result is shown in figure 6, and the result is found that: the two-dimensional code electrochromic device cannot be identified at 0V before and after circulation, and can be identified normally at +/-0.4V, so that the practical requirement is completely met.
3. Different driving power supplies drive two-dimensional code electrochromic device
As shown in fig. 7,20 mL of cola was added into a 50mL plastic container, the copper sheet and the zinc sheet were used as the positive and negative electrodes, respectively, a control switch was connected to the circuit, and then the two ends of the symmetric two-dimensional code electrochromic device prepared in example 1 were connected to the positive and negative electrodes, respectively, to form a loop. Under the same conditions, the cola was replaced with lemon and brine, and the results are shown in fig. 7.
The result shows that: when the circuit is disconnected, the electrochromic device for the symmetrical two-dimensional code displays colorless, and information in the electrochromic device cannot be obtained through scanning; when the circuit is closed and external voltages are arranged at two ends of the two-dimensional code electrochromic device, only one film presents magenta color after positive or negative voltages are applied, the symmetric two-dimensional code electrochromic device achieves decryption, and information in the symmetric two-dimensional code electrochromic device can be obtained through scanning.
4. Pattern switching for controlling patterned electrochromic devices through an external EC control module
Control software (such as doodling intelligence and the like) is downloaded on the wireless equipment, the signal receiving equipment is connected through wifi or Bluetooth, and the signal receiving equipment is externally connected with a solar cell panel of 1.5V and 75mW and the symmetrical two-dimensional code electrochromic device prepared in the embodiment 1. The solar panel is used as a power supply for driving the patterned electrochromic device, the signal receiving device can receive the instruction sent by the wireless device, and then control the output voltage direction of the solar panel so as to control the patterned electrochromic device to display different contents, as shown in fig. 8, and the result shows that the electrochromic device can control the display of the contents through the wireless device.
Claims (10)
1. A composition for preparing a patterned electrochromic device, wherein the composition consists of an electrochromic material, a photocrosslinker and a solvent;
the electrochromic material is poly (3, 3-bis ((2-ethylhexyl) oxy) methyl) -6, 8-dimethyl-3, 4-dihydro-2H-thieno [3,4-b ] [1,4] dioxaepine; the photocrosslinker is biaziridine photocrosslinker 2CNN.
2. The composition for preparing a patterned electrochromic device according to claim 1, wherein the mass ratio of the photocrosslinker to the electrochromic material is 1:1-3; the volume dosage of the solvent is 0.1-0.3 mL/mg based on the mass of the electrochromic material.
3. The composition for preparing a patterned electrochromic device according to claim 1, wherein the solvent is dichloromethane or chloroform.
4. Use of the composition of claim 1 for the preparation of a symmetric patterned electrochromic device, wherein the symmetric patterned electrochromic device structure is, in order, a first ITO substrate-a first patterned electrochromic layer-a gel electrolyte layer-a second patterned electrochromic layer-a second ITO substrate;
the symmetrical patterned electrochromic device is prepared as follows: (1) Under the condition of avoiding light, dissolving an electrochromic material and a photo-crosslinking agent in a solvent, uniformly mixing by ultrasonic, spraying a film on the conductive surface of ITO glass by using a spray gun, and marking as a first ITO substrate-first electrochromic film; preparing a second ITO substrate-a second electrochromic film by the same method; (2) Covering the surfaces of the electrochromic films of the first ITO substrate-first electrochromic film and the second ITO substrate-second electrochromic film prepared in the step (1) with a photomask, carrying out photocrosslinking under 365nm ultraviolet irradiation, and removing uncrosslinked parts by using dichloromethane to prepare a patterned electrochromic film, namely a first ITO substrate-first patterned electrochromic film and a second ITO substrate-second patterned electrochromic film; (3) And (3) adhering the peripheries of the first ITO substrate-first patterned electrochromic film, the first patterned electrochromic film layer of the second ITO substrate-second patterned electrochromic film and the second patterned electrochromic film layer by using 3M glue, forming a cavity in the middle, adding a proper amount of gel electrolyte into the cavity to form a gel electrolyte layer, dipping ethanol and dichloromethane in sequence, wiping by using cotton to remove redundant gel electrolyte, and then placing in a 60 ℃ oven for 3h to obtain the symmetrical patterned electrochromic device.
5. The use according to claim 4, wherein the mass ratio of photocrosslinker to electrochromic material in step (1) is 1:1-3; the volume dosage of the solvent is 0.1-0.3 mL/mg based on the mass of the electrochromic material.
6. The use according to claim 4, wherein the ultrasonic homogenization in step (1) is ultrasonic in a 50kHz ultrasonic machine for 10 minutes.
7. The method of claim 4, wherein the photocrosslinking in step (2) is carried out at 1000mW/cm 2 Is photocrosslinked for 90s under 365nm ultraviolet light irradiation.
8. The use of claim 4, wherein the photomask of step (2) comprises a two-dimensional code pattern.
9. The use of claim 4, wherein the gel electrolyte of step (3) is prepared as follows: swelling polymethyl methacrylate and polypropylene carbonate in oven at 60deg.C for 7 days to obtain substrate, adding LiBF 4 Mixing with acetonitrile and dichloromethane solution of ionic liquid, and spin-evaporating to remove solvent to obtain gel electrolyte; the added mass of the polymethyl methacrylate is 0.28-0.32 g/mL based on the volume of the polypropylene carbonate; the LiBF 4 The added mass of the catalyst is 0.04-0.041 g/mL based on the volume of the polypropylene carbonate; the ionic liquid is 1-n-butyl-3-methylimidazole trifluoromethane sulfonate; the added mass of the ionic liquid is 0.22-0.23 g/mL based on the volume of the polypropylene carbonate; the volume ratio of acetonitrile to dichloromethane is 1:1, a step of; the total volume of acetonitrile and dichloromethane is 0.4-0.6ml/ml based on the volume of polypropylene carbonate.
10. A symmetrical patterned electrochromic device prepared using the composition of claim 1, wherein the symmetrical patterned electrochromic device structure is, in order, a first ITO substrate-a first patterned electrochromic layer-a gel electrolyte layer-a second patterned electrochromic layer-a second ITO substrate.
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