CN116640418A - Electrochromic material and preparation method and application thereof - Google Patents
Electrochromic material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116640418A CN116640418A CN202310920545.3A CN202310920545A CN116640418A CN 116640418 A CN116640418 A CN 116640418A CN 202310920545 A CN202310920545 A CN 202310920545A CN 116640418 A CN116640418 A CN 116640418A
- Authority
- CN
- China
- Prior art keywords
- electrochromic material
- electrochromic
- layer
- cross
- combination
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 26
- 229940078552 o-xylene Drugs 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 13
- 229920000123 polythiophene Polymers 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- -1 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 4
- 125000004386 diacrylate group Chemical group 0.000 claims description 4
- 239000011245 gel electrolyte Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- VHFVKMTVMIZMIK-UHFFFAOYSA-N 1-(3-chlorophenyl)piperazine Chemical compound ClC1=CC=CC(N2CCNCC2)=C1 VHFVKMTVMIZMIK-UHFFFAOYSA-N 0.000 claims description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920001088 polycarbazole Polymers 0.000 claims description 2
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 229920000414 polyfuran Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000004984 smart glass Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 3
- NWIICCMMNLMQMY-UHFFFAOYSA-K 1-butyl-3-methylimidazol-3-ium phosphate Chemical compound [O-]P([O-])([O-])=O.CCCCn1cc[n+](C)c1.CCCCn1cc[n+](C)c1.CCCCn1cc[n+](C)c1 NWIICCMMNLMQMY-UHFFFAOYSA-K 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000002009 diols Chemical class 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 238000004132 cross linking Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 abstract description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical group [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 10
- 238000004528 spin coating Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000004971 Cross linker Substances 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- ABRVLXLNVJHDRQ-UHFFFAOYSA-N [2-pyridin-3-yl-6-(trifluoromethyl)pyridin-4-yl]methanamine Chemical compound FC(C1=CC(=CC(=N1)C=1C=NC=CC=1)CN)(F)F ABRVLXLNVJHDRQ-UHFFFAOYSA-N 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- VMZCDNSFRSVYKQ-UHFFFAOYSA-N 2-phenylacetyl chloride Chemical compound ClC(=O)CC1=CC=CC=C1 VMZCDNSFRSVYKQ-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000000206 photolithography Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 2
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- NDLIRBZKZSDGSO-UHFFFAOYSA-N tosyl azide Chemical compound CC1=CC=C(S(=O)(=O)[N-][N+]#N)C=C1 NDLIRBZKZSDGSO-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XDLDASNSMGOEMX-DNOMLBEFSA-N C1(=C(C(=C(C(=C1[2H])[2H])[2H])[2H])[2H])[2H].C1=CC=CC=C1 Chemical class C1(=C(C(=C(C(=C1[2H])[2H])[2H])[2H])[2H])[2H].C1=CC=CC=C1 XDLDASNSMGOEMX-DNOMLBEFSA-N 0.000 description 1
- 229920000144 PEDOT:PSS Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000002993 cycloalkylene group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- VDLYJFMBTUYWTO-UHFFFAOYSA-N ethanol;prop-2-enoic acid Chemical compound CCO.OC(=O)C=C.OC(=O)C=C VDLYJFMBTUYWTO-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000816 matrix-assisted laser desorption--ionisation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- 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
- G02F1/15165—Polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
-
- 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
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (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 provides an electrochromic material and a preparation method and application thereof, wherein the preparation raw materials of the electrochromic material comprise a combination of a color-changing material and a cross-linking agent, the cross-linking agent in the electrochromic material is extremely sensitive to ultraviolet light, a carbene group is easily generated under the condition of illumination so as to react with molecules containing an alkane group, and the activity of the cross-linking agent under the condition of no illumination is very low and the cross-linking agent does not react; therefore, the controllable cross-linking of the pixel array is realized under the condition of taking the fine film plate as a medium, and the cross-linking pixel array with any scale can be realized theoretically, so that the requirements of non-radiation display application are well met.
Description
Technical Field
The invention belongs to the technical field of printing display, and particularly relates to an electrochromic material and a preparation method and application thereof.
Background
Electrochromic refers to the phenomenon that the optical performance (transmittance, reflectivity and the like) of a device is changed stably and reversibly along with ion implantation and extraction under the action of an external electric field, and is mainly represented by reversible change of color and transparency. The material and the device have wide application prospects in the fields of electrochromic energy-saving intelligent windows, automobile rearview anti-dazzle mirrors, display devices, electronic paper, electrochromic skins and the like. The key difficulty that electrochromic materials cannot be further used for display applications is that the pixelized film forming process of the materials, namely, how to uniformly and widely realize the pixel array growth of the electrochromic materials with three primary colors becomes a key problem restricting the electrochromic passive display technology.
At present, a mode of screen printing an electrochromic layer is mainly adopted by the electrochromic layer of the pixel array, or a mode of forming a 3D network structure by introducing a free radical crosslinking agent for polymerization enhancement is mainly adopted, the current achievement is generally in millimeter magnitude, and the display device is difficult to meet; an electropolymerized pixel array (CN 115113449 a). In the large-area backboard pixel array scale, solute dilution occurs, so that the repeatability among batches is difficult to realize, the large-area backboard pixel array scale is not suitable for mass production, and the display application of display devices, electronic paper and the like is difficult to meet; the related application of display often needs a micrometer-scale pixel array, often the pixel scale is often controlled below 100 um x 100 um, and a large-area fine pixel array can be realized.
It is therefore increasingly important to develop an electrochromic material to meet alternative precision pixel array electrochromic layers.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an electrochromic material, a preparation method and application thereof, wherein the electrochromic material can realize controllable cross-linking of a pixel array under the condition of taking a fine film plate as a medium, and can realize cross-linking of the pixel array with any scale theoretically based on a used cross-linking agent, thereby meeting the requirements of non-radiation display application very well.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an electrochromic material, where the electrochromic material is prepared from a combination of a color-changing material and a crosslinking agent, where the crosslinking agent has a structure as shown in formula 1:
wherein R is 1 ，R 2 ，R 3 Each independently selected from the group consisting of hydrogen, halogen, substituted or unsubstituted alkyl having 1 to 40 carbon atoms (e.g., may be 1, 5, 10, 15, 20, 25, 30, 35, 40, and specific point values therebetween, to the extent and for brevity, the present invention is not limited to recitation of specific point values within the stated range), substituted or unsubstituted cycloalkyl having 3 to 70 carbon atoms (e.g., may be 3, 5, 10, 15, 20, 25, 30, 35, 40, and specific point values therebetween, to the extent and for brevity, the present invention is not limited to recitation of specific point values within the stated range), substituted or unsubstituted aryl having 6 to 30 carbon atoms (e.g., may be 6, 10, 15, 20, 25, 30, and specific point values therebetween), acyl having 1 to 40 carbon atoms (e.g., may be 1, 5, 10, 15, 20, 30, 35, 40, and for brevity, the present invention is not limited to recitation of specific point values within the stated range), acyl having 1 to 40 carbon atoms (e.g., may be 1, 5, 10, 15, 20, 25, 30, and for brevity, the present invention is not limited to recitation of specific point values within the range), and for brevity, the present invention is not limited to specific point values within the range, and for brevity, the specific point values within the rangeAnd 40, and the specific point values between the above-mentioned point values, the present invention is not exhaustive of the specific point values included in the range, substituted or unsubstituted cycloalkyl groups having 3 to 70 carbon atoms (for example, may be 1, 5, 10, 15, 20, 25, 30, 35, 40, and the specific point values between the above-mentioned point values), limited to the space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range, R is a substituted or unsubstituted alkylene group having 1 to 70 carbon atoms (for example, may be 1, 5, 10, 15, 20, 25, 30, 35, 40, and the specific point values between the above-mentioned point values, limited to the space and for the sake of brevity, the present invention is not exhaustive of the specific point values included in the range), and the substituents are each independently selected from phenyl groups, ester groups or amide groups having 1 to 40 carbon atoms (for example, may be 1, 5, 10, 15, 20, 25, 30, 35, and the specific point values between the above-mentioned point values, and the present invention is not limited to the concise range.
The alkylene group may be a linear alkylene group, a branched alkylene group or a cycloalkylene group.
The color-changing material comprises any one or a combination of at least two of polythiophene, polypyrrole, polyaniline, polyfuran, polycarbazole, polybenzazole and viologen.
In formula 1, the R 1 、R 2 、R 3 Each independently selected from phenyl or acyl, said R 4 Selected from hydrogen, ethyl or butyl, said R being selected from methylene or propylene.
The mass ratio of the color-changing material to the cross-linking agent is (2-100): 1, for example, may be 2: 1. 5: 1. 10: 1. 20: 1. 50: 1. 80: 1. 90: 1. 100:1, and specific point values between the above point values, are limited in space and for the sake of brevity, the present invention is not intended to exhaustively list the specific point values encompassed by the described range.
The crosslinking agent comprises any one or a combination of at least two of the compounds with the structures shown in the formulas 2-6.
。
The optical performance of the cross-linking agent is not obviously changed under the condition of solvent rinsing, the uncrosslinked part is fully dissolved and taken away by the solvent, the cross-linking agent is rapidly crosslinked under the ultraviolet light auxiliary condition (254 nm wavelength, 365 nm wavelength can be used), the solvent resistance is enhanced, the uncrosslinked part is not crosslinked, and the solubility is not changed.
In a second aspect, the present invention provides a method for preparing an electrochromic material according to the first aspect, the method comprising:
mixing the color-changing material, the cross-linking agent and the first solvent, coating the mixture on a substrate, drying, irradiating with ultraviolet light and developing to obtain the electrochromic material.
The first solvent comprises o-xylene and the substrate comprises a substrate with an ITO conductive layer, and the method of drying comprises vacuum drying, the temperature of the drying may be, for example, 25 c, 30 c, 35 c, 50 c, 80 c, 100 c, 101 c, 105 c, 108 c, 110 c, and specific point values between the above point values, are limited in scope and for brevity the present invention is not exhaustive list of the specific point values included in the range.
The drying time is 0.5-10 h, and may be, for example, 0.5 h, 1h, 2h, 5 h, 8 h, 10 h, and specific point values between the above point values, which are limited in space and for brevity, the present invention is not intended to be exhaustive.
The ultraviolet light has a wavelength of 254 nm or 365 nm.
The time of the ultraviolet irradiation is 1-10 min, for example, 1 min, 2 min, 5min, 8 min, 10 min, and specific point values among the above point values, which are limited in space and for the sake of brevity, the present invention does not exhaustively enumerate specific point values included in the range.
The ultraviolet irradiation is performed in a protective atmosphere, preferably a nitrogen atmosphere, and the developing includes developing with a second solvent including o-xylene for a period of time ranging from 20 to 30 s, such as 20 s, 22 s, 24 s, 26 s, 28 s, 30 s, and specific point values therebetween, and the present invention is not exhaustive of the list of specific point values included in the range for reasons of space and brevity.
The preparation method of the electrochromic material comprises the following steps: preparing a mixed solution from a color-changing material, a cross-linking agent and a first solvent, spin-coating the mixed solution onto an ITO conductive layer, vacuum-drying at room temperature for 30 min to form a film, attaching a film plate printed with a preset pattern onto the film, irradiating with 254 nm or 365 nm wavelength ultraviolet light for 5min in a nitrogen environment, and developing with o-xylene to obtain the electrochromic material.
Aiming at the technical difficulties in the film preparation process, the invention provides four steps of film coating, solvent volatilization, exposure and rinsing, and effectively solves the problems in the film preparation process. In the pixel array process of the invention, various different process modes are adopted, including but not limited to spin coating, blade coating, wire rod coating and the like, solvent volatilization is carried out in the modes of vacuum drying, heating annealing and the like, and exposure is carried out in the modes of ultraviolet irradiation, film shielding, laser direct engraving of patterns and the like. In the rinsing step, a solvent having a good effect such as xylene is selected as a cleaning liquid, and the unexposed and crosslinked portion is washed off and then dried, thereby achieving an excellent production effect.
In a third aspect, the present invention provides an electrochromic display device comprising a first substrate layer, a first electrode layer, an electrochromic material layer, an electrolyte layer, a counter electrode layer, a second substrate layer, arranged in that order, the electrochromic material layer comprising an electrochromic material as described in the first aspect.
The first substrate layer and the second substrate layer respectively and independently comprise any one or a combination of at least two of glass, polyethylene terephthalate or polyethylene naphthalate, the thickness of the first substrate layer is 0.1-1 mm, and the thickness of the second substrate layer is 0.1-1 mm.
The first electrode layer and the second electrode layer respectively and independently comprise any one or a combination of at least two of ITO electrodes, ag electrodes and IZO electrodes, the thickness of the first electrode layer is 100-110 nm, and the thickness of the second electrode layer is 100-110 nm.
The thickness of the electrochromic material layer is 130-150 nm.
The electrolyte layer comprises a gel electrolyte, wherein the gel electrolyte is prepared from polymer, solvent, ion solution, lithium salt and photoinitiator, the polymer comprises any one or combination of at least two of polymethyl methacrylate, polyvinylidene fluoride, polyethylene glycol diacrylate or polyethylene glycol dimethacrylate, the solvent comprises any one or combination of at least two of propylene carbonate, dimethyl carbonate, ethylene carbonate or water, the lithium salt comprises lithium perchlorate and/or lithium bistrifluoro-methylsulfonyl imide, the ion solution comprises 1-butyl-3-methylimidazole hexafluorophosphate, the photoinitiator comprises 2, 2-dimethoxy-2-phenyl acetophenone, and the electrolyte layer has a thickness of 100-110 um.
The counter electrode layer comprises any one or a combination of at least two of polythiophene such as poly (3, 4-ethylenedioxythiophene) -poly (styrenesulfonic acid), titanium dioxide or m-chlorophenylpiperazine, and has a thickness of 450-500 nm.
In a fourth aspect, the present invention provides a method for manufacturing an electrochromic display device as described in the second aspect, the method comprising:
and sequentially stacking the first substrate layer, the first electrode layer, the electrochromic material layer, the electrolyte layer, the counter electrode layer, the second electrode layer and the second substrate layer to obtain the electrochromic display device.
The first electrode layer and the second electrode layer can be formed into a film by means of film coating, sputtering, knife coating and the like.
The electrochromic material layer can be printed into a film by spin coating, spray coating, ink jet and the like.
The electrolyte layer may be coated to form a film by blade coating, screen printing, or the like.
The counter electrode layer can be printed into a film by spin coating, spray coating, ink jet and the like.
In a fifth aspect, the present invention provides an electrochromic material according to the first aspect for use in smart windows, military camouflage, dimming and toning, packaging displays.
Compared with the prior art, the invention has the following beneficial effects:
the cross-linking agent in the electrochromic material provided by the invention is extremely sensitive to ultraviolet light, and can easily generate a carbene group under the illumination condition so as to react with molecules containing an alkane group. And the activity of the cross-linking agent under the condition without illumination is very low, and the reaction can not occur. Thus realizing controllable cross-linking of the pixel array under the condition of taking a fine film plate as a medium. Meanwhile, based on the used cross-linking agent, a cross-linked pixel array with any dimension can be theoretically realized, and the requirements of non-radiation display application are well met.
Drawings
FIG. 1 is a graph showing the response of the film of example 3 to permeation over time during various cycles using 0.8V/5s, -0.6V/5 s as the driving voltage;
FIG. 2 is a graph showing maximum transmittance and minimum transmittance of the film of example 3 of the present invention in the color fading state and the color coloring state at different cycles, using 0.8V/5s, -0.6V/5 s as driving voltage;
FIG. 3 is a graph showing the full spectrum data of the absorption spectrum of the film of example 3 of the present invention in the initial and 300,000 cycles of the discolored state and the colored state using 0.8V/5s, -0.6V/5 s as the driving voltage;
FIG. 4 is a graph showing cyclic voltammetry characteristics of the device at 0 cycles for the electrochromic display device provided in application example 1;
fig. 5 is a cyclic voltammetry characteristic graph of the electrochromic display device provided in application example 1 at 10000 cycles;
FIG. 6 is a graph showing cyclic voltammetry characteristics of an electrochromic display device provided in application example 1 at 50000 cycles;
FIG. 7 is a graph showing cyclic voltammetry characteristics of an electrochromic display device provided in application example 1 at 150000 cycles;
FIG. 8 is a graph showing cyclic voltammetry characteristics of an electrochromic display device provided in application example 1 at 300000 cycles;
FIG. 9 is a diagram of the electrochromic material provided in example 3 after photolithography with different pattern plates;
FIG. 10 is a nuclear magnetic resonance hydrogen spectrum of the crosslinking agent compound provided in preparation example 1;
FIG. 11 is a nuclear magnetic resonance spectrum of the crosslinking agent compound provided in preparation example 1;
FIG. 12 is a mass spectrum of the crosslinking agent compound provided in preparation example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The experimental materials used in the examples and comparative examples of the present invention are as follows:
(1) PProDOT, poly 3, 4-propylpropene dioxythiophene (number average molecular weight 5000), autonomous synthesis by eplac;
(2) PEDOT: PSS, manufacturer, aikefa, brand, EL-P5015;
(3) ITO is common conductive glass in the market, can be purchased from a solar glass manufacturer in China, has a block resistance of 20 ohms/mouth and penetrates 80%;
(4) The materials used in the electrolyte are all commercial products commonly used in the market, PMMA (polymethyl methacrylate, number average molecular weight of 150,000, CAS:) PEGDA (poly ethanol diacrylate, number average molecular weight: 600, cas: />) Photoinitiator (dimethoxy-2-phenylacetophenone, CAS: />) PC (propylene carbonate,)>) LiTFSI (lithium bis-trifluoromethanesulfonyl imide, CAS: />) Purchased from alaa Ding Pingtai;
preparation 1 materials used in preparation (5) were commercially available, triethylamine (CAS: 121-44-8), methylene chloride (CAS:4-Methylbenzenesulfonyl stack (CAS: 941-55-9), acetonitrile (CAS: 75-05-8), anhydrous sodium sulfate (CAS: 7757-82-6), phenylacetyl chloride (CAS: 103-80-0) were purchased from the exploration platform; trimethylolpropane (CAS:>) Purchased from alaa Ding Pingtai.
Preparation example 1
The preparation example provides a cross-linking agent compound 1-1, wherein the compound 1-1 is prepared according to the preparation method described in CN 114478306A:
into a 500mL three-necked round bottom flask, 6.7g of raw material 1 and 30.4g of triethylamine were added, and 200mL of methylene chloride was added as a solvent, and the reaction system was stirred in an ice salt bath for 10 minutes under the protection of argon. Subsequently, 34.8g of phenylacetyl chloride was slowly added into the reaction system through a constant pressure titration funnel, after the addition was completed, the ice salt bath was removed, the reaction was continued for 24 hours while monitoring with TCL, the reaction was completed, water was added to quench the reaction, extraction was performed using methylene chloride, the organic phases were combined, dried using anhydrous sodium sulfate, and filtered to obtain a crude product. The crude product was purified by column chromatography using silica gel to give intermediate 1-1 as a white solid (14.2 g, yield 58.3%). 9.8g of intermediate 1-1 and 16.6g of 4-methylbenzenesulfonyl azide are added into a three-neck flask, 9.1g of triethylamine is added as a base, acetonitrile is added as a solvent, the reaction is carried out at room temperature for 24 hours, meanwhile, TCL is used for monitoring, water quenching reaction is added after the reaction is finished, dichloromethane is used for extraction, organic phases are combined, anhydrous sodium sulfate is used for drying, and a crude product is obtained through filtration. The crude product was subjected to column chromatography using silica gel, and compound 1-1 (8.5 g, yield 75.3%) was isolated.
Preparation example 1 was tested using Bruker 400 MHz nuclear magnetic resonance (Bruker) and the nuclear magnetic resonance hydrogen spectrum is shown in FIG. 10, 1H NMR (400 MHz, deuterated Benzene Benzene-d 6) delta 7.42-7.37 (m, 6H), 7.09 (dd, J=8.4, 7.4 Hz, 6H), 6.93-6.86 (m, 3H), 4.14 (s, 6H), 1.22 (q, J=7.6 Hz, 2H), 0.64 (t, J=7.5 Hz, 3H).
The crosslinker compound 1-1 described in preparation example 1 was tested using Bruker 400 MHz nuclear magnetic resonance, the nuclear magnetic resonance spectrum is shown in FIG. 11, 13 C NMR (101 MHz, Benzene-d6) δ 164.23, 129.17, 126.03, 125.66, 124.24, 64.53, 63.60, 41.67, 23.72, 7.48。
the crosslinker compound 1-1 described in preparation 1 was tested using a Finnigan GCQ mass spectrometer, the mass spectrum is shown in FIG. 12, TOF-MS (MALDI, M/z) [ M]Calculated value C 30 H 26 N 6 O 6 566.19, test value 568.38.
Example 1
The embodiment provides an electrochromic material, and the preparation raw materials of the electrochromic material include: 120 mg PProDOT (polythiophene), 2.4. 2.4 mg crosslinker (preparation example 1), 4. 4 mL o-xylene.
The preparation method of the electrochromic material comprises the following steps: 1. and (3) coating, namely mixing PPro DOT, a cross-linking agent and o-xylene, spin-coating the mixture on an ITO layer, wherein the spin-coating speed is 1000 r/min, 2. Volatilizing a solvent, vacuum drying at room temperature for 30 min,3. Exposing, attaching a film plate printed with a preset pattern on the film after forming the film, irradiating for 5min by using 254 nm wavelength ultraviolet light in a nitrogen environment, 4. Developing, and developing by using o-xylene to obtain the electrochromic material.
Example 2
This example provides an electrochromic material which differs from example 1 only in that 120 mg PProDOT (polythiophene), 4 mg crosslinker (preparation 1), 4 mL solvent o-xylene; the kinds, amounts and preparation methods of the other components were the same as in example 1.
Example 3
This example provides an electrochromic material which differs from example 1 only in that 120 mg PProDOT (polythiophene), 6 mg crosslinker (preparation 1), 4 mL solvent o-xylene; the kinds, amounts and preparation methods of the other components were the same as in example 1. The electrochromic material takes 0.8V/5s, -0.6V/5 s as driving voltage, and a data graph of permeation response with time in different cycles is shown in fig. 1; the electrochromic material takes 0.8V/5s, -0.6V/5 s as driving voltage, and the maximum transmittance of the fading state and the minimum transmittance of the coloring state in different cycles are shown in the graph of FIG. 2; the full spectrum data graph of the absorbance spectrum in the bleached state and the colored state at the initial and the cycles 300,000 is shown in fig. 3, with 0.8V/5s, -0.6V/5 s as the driving voltage.
Example 4
This example provides an electrochromic material which differs from example 1 only in that 120 mg PProDOT (polythiophene), 12 mg crosslinker (preparation 1), 4 mL solvent o-xylene; the kinds, amounts and preparation methods of the other components were the same as in example 1.
Example 5
This example provides an electrochromic material which differs from example 1 only in that 120 mg PProDOT (polythiophene), 24 mg crosslinker (preparation 1), 4 mL solvent o-xylene; the kinds, amounts and preparation methods of the other components were the same as in example 1.
Example 6
The embodiment provides an electrochromic material, and the preparation raw materials of the electrochromic material include: 120 mg PProDOT (polythiophene), 2.4. 2.4 mg crosslinker (preparation example 1), 4. 4 mL o-xylene.
The preparation method of the electrochromic material comprises the following steps: mixing PPro DOT, a cross-linking agent and o-xylene, spin-coating the mixture onto an ITO layer at a spin-coating speed of 1000 rpm, vacuum drying at room temperature for 30 min to form a film, attaching a film plate printed with a preset pattern onto the film, irradiating the film plate with 365 and nm-wavelength ultraviolet light for 10 min in a nitrogen environment, and developing with o-xylene to obtain the electrochromic material.
Comparative example 1
The comparative example provides an electrochromic material, the electrochromic material is prepared from the following raw materials: 120 mg PProDOT (polythiophene), 4 mL o-xylene.
The preparation method of the electrochromic material comprises the following steps: and mixing PPro DOT and o-xylene, spin-coating the mixture onto an ITO layer, wherein the spin-coating speed is 1000 rpm, drying the mixture at room temperature for 30 min in vacuum to form a film, attaching a film plate printed with a preset pattern onto the film, and developing the film plate by using o-xylene to obtain the electrochromic material, wherein the electrochromic material is completely cleaned and removed.
Application example 1
The application example provides a preparation method of an electrochromic display device, which comprises the following steps:
ITO was sputtered on the first base layer (thickness: 1 mm) as the first electrode layer 110 nm, a PProdot crosslinked film (preparation method in example 3) was prepared on the first electrode layer (thickness: 110 nm) to have a thickness of 130 nm, to obtain a substrate 1, ITO was sputtered on the second base layer (thickness: 1 mm) as the second electrode layer (thickness: 110 nm) to prepare PEDOT (5015) (thickness: 500 nm) by a screen printing method, to obtain a substrate 2, 3g of polymethyl methacrylate, 5g of polycarbonate, 5g of polyethylene glycol diacrylate, 2.8g of LiTFSI, and 15, 2-dimethoxy-2-phenylacetophenone of 15 mg were respectively weighed, stirred uniformly to obtain an electrolyte slurry, the electrolyte slurry was drawn to a set height by a 3M paste, and the substrate 1 and the substrate 2 were bonded by a screen printing method to obtain an electrochromic device. The cyclic voltammetry characteristic curve graph of the electrochromic device at 0 times of cycle times is shown in fig. 4; cyclic voltammetry characteristic curve of the device at 10000 cycles, as shown in fig. 5; a cyclic voltammogram of the device at 50000 cycles as shown in fig. 6; cyclic voltammetry characteristic graph of the device at 150000 cycles as shown in fig. 7; cyclic voltammetry characteristic of the device at 300000 cycles as shown in fig. 8; the electrochromic material provided in example 3 is subjected to photolithography in different pattern films, as shown in fig. 9.
Application example 2
The application example provides a preparation method of an electrochromic display device, which comprises the following steps:
ITO was sputtered on the first base layer (thickness: 1 mm) as the first electrode layer 110 nm, patterning by photolithography mask was added on the first electrode layer (thickness: 110 nm), a PProDOT crosslinked film (preparation method in example 6) was prepared to a thickness of 200 nm, to obtain a substrate 1, ITO was sputtered on the second base layer (thickness: 1 mm) as the second electrode layer (thickness: 110 nm), PEDOT (5015) (thickness: 500 nm) was prepared by screen printing method, to obtain a substrate 2, 3g of polymethyl methacrylate, 5g of polycarbonate, 5g of polyethylene glycol diacrylate, 2.8g of LiTFSi, and 15 mg of 2, 2-dimethoxy-2-phenylacetophenone were weighed, stirred uniformly to obtain an electrolyte paste, the electrolyte paste was spread on the PEDOT film (thickness: 100 um) by a 3M paste to a set height, and the above substrate 1 and substrate 2 were bonded to each other, to obtain an electrochromic device.
The electrochromic materials provided in examples 1-6 and comparative example 1 were tested for performance by the following method:
(1) Absorption intensity: the sample obtains absorption intensity at 550nm wavelength;
(2) Solvent resistance: the sample test calculation was performed by comparing the ultraviolet absorption spectrum intensity variation with the solvent resistance, and the absorption intensity obtained at 550nm wavelength in the example;
(3) Testing microscopic dimensions by a 3D microscope and a laser confocal microscope;
the test results are shown in Table 1.
The electrochromic display device provided in application example 1 was subjected to performance test, and the specific method is as follows:
the response speed, the cycling stability and the charge capacity change of a device are tested by using an electrochemical workstation and an ultraviolet absorption spectrometer;
the test results are shown in Table 2.
As can be seen from the data in table 1, the pattern size of the electrochromic material provided in example 3 of the present invention is about 50 a um a.
As can be seen from the data in Table 2, the electrochromic display device provided by the invention has cycling stability exceeding thirty-thousand times, and the change of the transmission contrast is always 30%, and almost no loss is caused.
The applicant states that the process of the invention is illustrated by the above examples, but the invention is not limited to, i.e. does not mean that the invention must be carried out in dependence on the above process steps. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of selected raw materials, addition of auxiliary components, selection of specific modes, etc. fall within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The electrochromic material is characterized in that the preparation raw materials of the electrochromic material comprise a combination of the electrochromic material and a cross-linking agent, and the cross-linking agent has a structure shown in a formula 1:wherein R is 1 ，R 2 ，R 3 Each independently selected from hydrogen, halogen, substituted or unsubstituted alkyl having 1 to 40 carbon atoms, substituted or unsubstituted cycloalkyl having 3 to 70 carbon atoms, substituted or unsubstituted aryl having 6 to 30 carbon atoms, acyl having 1 to 40 carbon atoms, R 4 Selected from hydrogen, substituted or unsubstituted alkyl groups having 1 to 70 carbon atoms, substituted or unsubstituted rings having 3 to 70 carbon atomsAlkyl, R is a substituted or unsubstituted alkylene group containing 1 to 70 carbon atoms, and each of the substituted substituents is independently selected from phenyl, an ester group of 1 to 40 carbon atoms, or an amide group.
2. The electrochromic material according to claim 1, characterized in that the color-changing material comprises any one or a combination of at least two of polythiophene, polypyrrole, polyaniline, polyfuran, polycarbazole, polyindole or viologen;
in formula 1, the R 1 、R 2 、R 3 Each independently selected from phenyl or acetyl, said R 4 Selected from hydrogen, ethyl or butyl, said R being selected from methylene or propylene;
the mass ratio of the color-changing material to the cross-linking agent is (2-100): 1.
3. the electrochromic material according to claim 1, characterized in that the crosslinking agent comprises any one of compounds of the structure shown in any one of formulae 2 to 6 or a combination of at least two thereof;
。
4. a method of preparing an electrochromic material according to any one of claims 1 to 3, comprising:
mixing the color-changing material, the cross-linking agent and the first solvent, coating the mixture on a substrate, drying, irradiating with ultraviolet light, and developing to obtain the electrochromic material.
5. The method of claim 4, wherein the first solvent comprises o-xylene, the substrate comprises a substrate with an ITO conductive layer, the drying method comprises vacuum drying, the drying temperature is 25-110 ℃, the drying time is 0.5-10 h, the ultraviolet irradiation has a wavelength of 254-nm or 365-nm, the ultraviolet irradiation has a time of 1-10 min, the ultraviolet irradiation is performed in a protective atmosphere, the developing comprises developing with a second solvent, the second solvent comprises o-xylene, and the developing time is 20-30 s.
6. An electrochromic display device comprising a first substrate layer, a first electrode layer, an electrochromic material layer, an electrolyte layer, a counter electrode layer, a second substrate layer, which are arranged in this order, wherein the electrochromic material layer comprises the electrochromic material of any one of claims 1-3.
7. The electrochromic display device of claim 6 wherein the first and second substrate layers each independently comprise any one or a combination of at least two of glass, polyethylene terephthalate, or polyethylene naphthalate, and the first and second electrode layers each independently comprise any one or a combination of at least two of ITO, ag, or IZO electrodes.
8. The electrochromic display device according to claim 6, wherein the electrolyte layer comprises a gel electrolyte, the gel electrolyte being prepared from a raw material comprising a polymer comprising any one or a combination of at least two of polymethyl methacrylate, polyvinylidene fluoride, polyethylene glycol (diol) diacrylate or polyethylene glycol dimethacrylate, a solvent comprising any one or a combination of at least two of propylene carbonate, dimethyl carbonate, ethylene carbonate or water, an ionic solution comprising lithium perchlorate and/or lithium bistrifluoromethylsulfonyl imide, a lithium salt comprising 1-butyl-3-methylimidazolium phosphate, and a photoinitiator comprising 2, 2-dimethoxy-2-phenylacetophenone, the counter electrode layer comprising any one or a combination of at least two of polythiophene, titanium dioxide or m-chlorophenylpiperazine.
9. A method of manufacturing an electrochromic display device as claimed in any one of claims 6 to 8, characterized in that the method of manufacturing comprises the steps of:
and sequentially stacking the first substrate layer, the first electrode layer, the electrochromic material layer, the electrolyte layer, the counter electrode layer, the second electrode layer and the second substrate layer to obtain the electrochromic display device.
10. Use of an electrochromic material according to any one of claims 1-3 in smart windows, military camouflage, dimming and toning, packaging displays.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310920545.3A CN116640418B (en) | 2023-07-26 | 2023-07-26 | Electrochromic display device and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310920545.3A CN116640418B (en) | 2023-07-26 | 2023-07-26 | Electrochromic display device and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116640418A true CN116640418A (en) | 2023-08-25 |
| CN116640418B CN116640418B (en) | 2023-11-03 |
Family
ID=87615668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310920545.3A Active CN116640418B (en) | 2023-07-26 | 2023-07-26 | Electrochromic display device and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116640418B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170025612A (en) * | 2015-08-31 | 2017-03-08 | 한밭대학교 산학협력단 | Microporous polymer membrane for electrochromic device and smart window including the same |
| CN113336666A (en) * | 2021-05-26 | 2021-09-03 | 复旦大学 | Universal cross-linking agent and synthesis method and application thereof |
| CN114478306A (en) * | 2022-01-27 | 2022-05-13 | 苏州欧谱科显示科技有限公司 | Multi-arm diazo compound and preparation method and application thereof |
-
2023
- 2023-07-26 CN CN202310920545.3A patent/CN116640418B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170025612A (en) * | 2015-08-31 | 2017-03-08 | 한밭대학교 산학협력단 | Microporous polymer membrane for electrochromic device and smart window including the same |
| CN113336666A (en) * | 2021-05-26 | 2021-09-03 | 复旦大学 | Universal cross-linking agent and synthesis method and application thereof |
| CN114478306A (en) * | 2022-01-27 | 2022-05-13 | 苏州欧谱科显示科技有限公司 | Multi-arm diazo compound and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116640418B (en) | 2023-11-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2587079C2 (en) | Stable electrochromic module | |
| KR102035332B1 (en) | Electrochromic Compounds, Electrochromic Compositions, and Electrochromic Display Elements | |
| JP4782127B2 (en) | Electrolyte containing eutectic mixture and electrochromic device using the same | |
| JP6874389B2 (en) | Electrochromic compounds, electrochromic compositions and electrochromic devices | |
| EP1953575A1 (en) | Light control material and light control film | |
| KR101812880B1 (en) | Water-soluble diacetylene monomer, composition for photolithography containing water-soluble diacetylene monomer and pedot/pss conductive polymers, and method for preparing micropattern using the same | |
| EP0444201A1 (en) | Method of producing a color filter | |
| Kobayashi et al. | Conducting polymer image formation with photoinduced electron transfer reaction | |
| CN114907551B (en) | Red electrochromic polymer, preparation method, film and device | |
| CN108873537A (en) | A kind of electrochomeric films, preparation method and application and electrochromic device | |
| KR20030069082A (en) | Transparent Polythiophene Layers of High Conductivity | |
| CN116640418B (en) | Electrochromic display device and preparation method thereof | |
| KR20090127732A (en) | New thiophen compounds, thiophen polymer,conductive high polymer film and forming method of conductive high polymer pattern using thereof | |
| CN108251099A (en) | Under a kind of illumination can gelation and selfreparing electrochromic solutions and its application | |
| CN114957275B (en) | Organic small molecule electrochromic material, film and device and preparation method thereof | |
| Huang et al. | Photolithographically patterned and highly stable electrochromic displays enabled by a photo-assisted cross-linker | |
| KR102421885B1 (en) | Hybrid electrochromic material, manufacturing method thereof and electrochromic device comprising the same | |
| JPH03208689A (en) | Optical data recording medium and preparation thereof | |
| KR100934645B1 (en) | Photochromic diaryethene compounds capable of oxidative polymerization, diarylethene polymer compositions containing them and nanostructures containing them | |
| CN111393616A (en) | Black electrochromic polymer, preparation thereof and electrochromic polymer film | |
| JPS63196682A (en) | Electrochromic display material | |
| KR20230115842A (en) | Photo-curable electrochromic material, electrochromic device comprising same, and method for manufacturing same | |
| JPS6337119A (en) | Novel electrolytic polymer and electrochromic display element obtained by using said polymer | |
| CN117384361A (en) | Soluble polythiophene derivative electrochromic material and preparation method thereof | |
| KR20040103008A (en) | Preparation of nanoelectrochromic films and electrochromic devices therefrom |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |