CN105694842A - Electrochromic material, preparation method thereof, black electrochromic material and preparation method thereof - Google Patents
Electrochromic material, preparation method thereof, black electrochromic material and preparation method thereof Download PDFInfo
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- CN105694842A CN105694842A CN201610153786.XA CN201610153786A CN105694842A CN 105694842 A CN105694842 A CN 105694842A CN 201610153786 A CN201610153786 A CN 201610153786A CN 105694842 A CN105694842 A CN 105694842A
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 76
- 239000011521 glass Substances 0.000 claims description 59
- 239000010409 thin film Substances 0.000 claims description 32
- 239000010408 film Substances 0.000 claims description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 11
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 239000006255 coating slurry Substances 0.000 claims description 7
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 6
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000000712 assembly Effects 0.000 claims description 4
- 238000000429 assembly Methods 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 claims description 3
- 238000005562 fading Methods 0.000 abstract description 8
- 238000002834 transmittance Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- -1 triphenyl amine compound Chemical class 0.000 description 8
- 208000035126 Facies Diseases 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- JKJWYKGYGWOAHT-UHFFFAOYSA-N bis(prop-2-enyl) carbonate Chemical group C=CCOC(=O)OCC=C JKJWYKGYGWOAHT-UHFFFAOYSA-N 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- XVXGYZFARCOVHS-BINOZUKVSA-N (7s,9s)-7-[(2r,4s,5s,6s)-4-amino-5-hydroxy-6-methyloxan-2-yl]oxy-6,9,11-trihydroxy-9-(2-hydroxyacetyl)-8,10-dihydro-7h-tetracene-5,12-dione Chemical compound C1[C@H](N)[C@H](O)[C@H](C)O[C@H]1O[C@@H]1C2=C(O)C(C(=O)C3=CC=CC=C3C3=O)=C3C(O)=C2C[C@@](O)(C(=O)CO)C1 XVXGYZFARCOVHS-BINOZUKVSA-N 0.000 description 1
- QQIOJAHQDFJQSJ-UHFFFAOYSA-N 1-bromo-4-(1-bromoethyl)benzene Chemical compound CC(Br)C1=CC=C(Br)C=C1 QQIOJAHQDFJQSJ-UHFFFAOYSA-N 0.000 description 1
- YCQVNMKLANFADW-UHFFFAOYSA-N 2-bromoethyl diethyl phosphate Chemical compound CCOP(=O)(OCC)OCCBr YCQVNMKLANFADW-UHFFFAOYSA-N 0.000 description 1
- 0 CN(C)c(cc1)ccc1N(c1ccc(*)cc1)c1ccc(CP(O)(O)=O)cc1 Chemical compound CN(C)c(cc1)ccc1N(c1ccc(*)cc1)c1ccc(CP(O)(O)=O)cc1 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3882—Arylalkanephosphonic acids
-
- 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
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1014—Carbocyclic compounds bridged by heteroatoms, e.g. N, P, Si or B
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
The invention provides an electrochromic material, a preparation method thereof, a black electrochromic material and a preparation method thereof. The electrochromic material has the structure in the formula (I), serves as an electrochromic material of a counter electrode to be matched with a compound serving as an electrochromic material of a work electrode, the compound has the structure in the formula (IV), and the electrochromic material and the compound are assembled to obtain an electrochromic device. The device is black in the colored state and is light yellow in the fading state. The device is high in transmittance difference and good in circulation stability and can be widely used in devices such as electrochromic windows, rearview mirrors and electrochromic displayers.
Description
Technical field
Off-color material field, field of the present invention, particularly relates to a kind of electrochromic material and preparation method thereof and black electrochromic material and preparation method thereof。
Background technology
Electrochromism (Electrochromism, EC) refer to that the phenomenon of stable, reversible color change occurs under the effect of extra electric field for the optical properties (reflectance, transmitance, absorbance etc.) of material, show as the reversible change of color and transparency in appearance。The material with electrochromic property is called electrochromic material, and the device made with electrochromic material is called electrochromic device。Electrochromic material is one of focus of material science research in recent years。Electrochromic material is the important component part in electrochromic device, dominates the electrochromic property of device。According to the structural property of material, electrochromic material can be divided into anode electrochromic material (ion embeds painted) and cathode electrochromic material (ion is extracted out painted)。Anode electrochromic material and cathode electrochromic material can be assembled into complementary type electrochromic device, and this type of complementary devices can improve the electrochromic property of entirety, and such as optical contrast, color changes, spectral absorption scope etc.。
At present, a lot of seminars have been developed that electrochromic material and the device of multiple color, and black electrochromic material and device are always up the difficult problem that researcher needs to capture。At present, the preparation method of disclosed black electrochromic device mainly has two kinds: the first utilizes the black polymer of the single working electrode of method preparation of chemical copolymerization；Its two be utilize two or more polymer by color addition to obtain black electrochromic device so that it is can all absorb in visible region。But, by the unstable chemcial property of the electrochromic material in the black electrochromic device that said method prepares, the optical contrast of device is low, and cyclical stability is poor, and then limits its application in actual production。
Summary of the invention
In view of this, the technical problem to be solved is in that to provide a kind of electrochromic material and preparation method thereof and black electrochromic device and preparation method thereof, the stable in properties of off-color material in black electrochromic device provided by the invention, and transmitance difference is high, good cycling stability。
The invention provides a kind of electrochromic material, there is formula (I) structure,
The preparation method that present invention also offers a kind of electrochromic material of the present invention, including:
It is formula (I) compound by formula (II) converting compounds,
Preferably, the compound of described formula (II) structure prepares in accordance with the following methods:
Formula (III) compound is reacted with p-bromobenzaldehyde, obtains formula (II) compound,
Present invention also offers a kind of black electrochromic device, including the TCO glassy layer contacted successively, working electrode thin layer, dielectric layer, to electrode thin film layer and TCO glassy layer；
Described is formula (I) compound to the electrochromic material in electrode thin film layer；
Electrochromic material in described working electrode thin layer is formula (IV) compound；
Preferably, the material of described working electrode thin layer is the titanium deoxid film of adsorption-type (IV) compound。
Preferably, the described material to electrode thin film layer is the titanium deoxid film of adsorption-type (I) compound。
Preferably, the TCO glass of described TCO glassy layer is indium tin oxide-coated glass, zinc oxide aluminum electro-conductive glass or fluoride doped indium tin oxide electro-conductive glass。
The preparation method that present invention also offers a kind of black electrochromic device of the present invention, including:
1) preparation work electrode thin film layer on TCO glassy layer, obtains being covered with the TCO glass of working electrode thin layer；
Prepared by TCO glassy layer to electrode thin film layer, obtain being covered with the TCO glass to electrode thin film layer；
2) by being covered with the TCO glass of working electrode thin layer, dielectric layer, being covered with the TCO glass assemblies to electrode thin film layer, black electrochromic device is obtained；
Described is formula (I) compound to the electrochromic material in electrode thin film layer；
Electrochromic material in described working electrode thin layer is formula (IV) compound；
Preferably, it is covered with the TCO glass to electrode thin film layer described in specifically to prepare in accordance with the following methods:
1-1-a) titanium dioxide coating slurry on TCO glass, obtains being attached with the TCO glass of titanium deoxid film；
1-2-a) by being attached with the TCO glass-impregnated of titanium deoxid film in the dichloromethane solution containing formula (I) compound, obtain being covered with the TCO glass to electrode thin film layer。
Preferably, the TCO glass being covered with working electrode thin layer described in specifically prepares in accordance with the following methods:
1-1-b) titanium dioxide coating slurry on TCO glass, obtains being attached with the TCO glass of titanium deoxid film；
1-2-b) by being attached with the TCO glass-impregnated of titanium deoxid film at the aqueous solution containing formula (IV) compound, obtain being covered with the TCO glass of working electrode thin layer。
Compared with prior art, the invention provides a kind of triphenyl amine compound electrochromic material and preparation method thereof and black electrochromic device and preparation method thereof, electrochromic material provided by the invention has formula (I) structure, and it is mutually matched as the compound of the off-color material to electrode with formula (IV) structure as working electrode off-color material, common assembling obtains electrochromic device, the coloured state of this device is black, and state of fading is faint yellow；And the transmitance of this device is high, good cycling stability, can be widely used for the devices such as electrochromic, rearview mirror and color changing display, test result indicate that, the transmitance difference of black electrochromic device provided by the invention may be up to 60%, and this device cycle 120,000 times, its performance decays hardly。Additionally, the preparation method of this black electrochromic device is simple, it may be achieved industrialized production。
Accompanying drawing explanation
Fig. 1 is the structural representation of black electrochromic device of the present invention；
Fig. 2 is the compound (PBT) shown in formula (IV) that the embodiment of the present invention 1 prepares1H nuclear magnetic resonance, NMR (1HNMR) spectrogram；
Fig. 3 is Fourier transform infrared (FT-IR) spectrogram of the compound (PBT) shown in formula (IV) that the embodiment of the present invention 1 prepares；
Fig. 4 is the compound (DBP) shown in formula (I) that the embodiment of the present invention 2 prepares1H nuclear magnetic resonance, NMR (1HNMR) spectrogram；
Fig. 5 is Fourier transform infrared (FT-IR) spectrogram of the compound (DBP) shown in formula (I) that the embodiment of the present invention 2 prepares；
Fig. 6 is the structure principle chart of black electrochromic device of the present invention；
Fig. 7 is the cyclic voltammetry curve of the device that the embodiment of the present invention prepares；
Fig. 8 is that the device for preparing of the embodiment of the present invention is respectively in the transmitance of coloured state and state of fading；
Fig. 9 be the coloured state of the device that the embodiment of the present invention prepares and state of fading through rate variance；
Figure 10 is the variation diagram that the device that the embodiment of the present invention prepares circulates the coloured state after different number of times and state transmitance of fading continuously。
Detailed description of the invention
The invention provides a kind of electrochromic material, there is formula (I) structure,
The off-color material with (I) structure provided by the invention, can be applicable to the preparation of black electrochromic device, and the black electrochromic device prepared can all absorb visible ray when coloured state, and reaches complete black。
Present invention also offers the preparation method of electrochromic material shown in a kind of formula (I), including:
It is formula (I) compound by formula (II) converting compounds,
According to the present invention, formula (II) converting compounds is formula (I) compound by the present invention, and concrete, the present invention preferably concretely comprises the following steps:
A) first formula (II) compound is reacted with reducing agent, obtain formula (II-1) compound；
B) it is then formula (I) compound by formula (II-1) converting compounds again；
Wherein, the reducing agent in described step a) is preferably sodium borohydride；In described step b), formula (II-1) compound is preferably reacted by the present invention with zinc bromide and NSC 5284, obtain the compound containing phosphate ester, then the ester group on phosphate ester is being hydrolyzed in acid condition, obtain formula (I) compound。
Formula of the present invention (II) compound is preferably and is reacted with p-bromobenzaldehyde by formula (III) compound, obtains formula (II) compound, and wherein, the catalyst of described reaction is preferably Pd2(dba)3And Cs2CO3。
Formula of the present invention (III) compound prepares preferably by by bromo-for 4-DMA and P-nethoxyaniline hybrid reaction, and the catalyst of described reaction is preferably Pd2(dba)3。
Present invention also offers a kind of black electrochromic device, including the TCO glassy layer contacted successively, working electrode thin layer, dielectric layer, to electrode thin film layer and TCO glassy layer；
Described is formula (I) compound to the electrochromic material in electrode thin film layer；
Electrochromic material in described working electrode thin layer is formula (IV) compound；
In the present invention, described TCO (TransparentConductiveOxide) glass is that the glass plating the conductive oxide film of layer of transparent uniformly by physically or chemically film plating process at surface of plate glass is referred to as TCO glass。In the present invention, described TCO glass is preferably ITO (indium tin oxide-coated glass), AZO (zinc oxide aluminum electro-conductive glass) or FTO (fluoride doped indium tin oxide electro-conductive glass), more preferably FTO glass。
In the present invention, the material of described working electrode thin layer is the titanium deoxid film of adsorption-type (IV) compound。The present invention compound (1 to formula (IV) structure; double; two [((the N-phosphono-2-ethyl)-4 of 4-; 4'-bipyridyl)-methyl]-benzene tetrachloride; be abbreviated as PBT) source there is no particular/special requirement, those skilled in the art directly can prepare according to existing report。
The electrolyte of described dielectric layer is preferably Allyl carbonate and the ethylene carbonate mixed solution of lithium hexafluoro phosphate；Wherein, the concentration of lithium hexafluoro phosphate is preferably the volume ratio of 0.1～0.5mol/L, Allyl carbonate and ethylene carbonate and is preferably 1～2: 1。
In the present invention, the described material to electrode thin film layer is the titanium deoxid film of adsorption-type (I) compound (4-N, N dimethyl-4 '-methoxyl group-triphenylamine base methylene phosphonic acid, be abbreviated as DBP)。
Black electrochromic device provided by the invention, by the compound of the compound and formula (IV) structure that select specific formula (I) structure respectively as the electrochromic material to electrode and working electrode, make the electrochromic device prepared be capable of the whole of visible ray when coloured state to absorb, so that it presents complete black, and the optical contrast of this device is high, namely transmitance difference is high, and good cycling stability。Additionally, by by described electrochromic material by being chemisorbed on titanium deoxid film of the present invention, and then make the response time of device obtained fast, driving voltage is low。
Concrete, the structural representation of electrochromic device of the present invention is as it is shown in figure 1, structural representation that Fig. 1 is black electrochromic device of the present invention；Its operation principle is as follows:
When switch A is in closure state, and when B is in open-circuit condition, electric current is propagated clockwise along wire。Working electrode obtains electronics, and viologen compound is changed to positive monovalent cation free radical by the positive cationic state of bivalence, is changed into navy blue state from pellucidity；Now, to electrode owing to obtaining the electronics of equivalent, there is redox reaction, be also changed into yellow green state from pellucidity。And in electrolyte now, owing to the electric charge gain and loss of electrode surface, lithium ion and hexafluorophosphoricacid acid ions shift to working electrode and respectively to electrode。Now, device is in colored state。
When device is in colored state, opening switch B, Guan Bi switch A, electric current is just along wire counterclockwise flow。Working electrode loses electronics, and the viologen compound being in navy blue positive monovalent cation free radical state is oxidized to transparent positive bivalent cation, and to electrode material generation reduction reaction, yellow green state takes off to colorless state。Now, device is in pellucidity。
So, just achieve device painted by being clear to, then by the painted conversion to pellucidity。
The preparation method that present invention also offers a kind of black electrochromic device of the present invention, including:
1) prepare the working electrode thin layer on TCO glassy layer, obtain being covered with the TCO glass of working electrode thin layer；
Prepare on TCO glassy layer to electrode thin film layer, obtain being covered with the TCO glass to electrode thin film layer；
2) by being covered with the TCO glass dielectric layer of working electrode thin layer, being covered with the TCO glass assemblies to electrode thin film layer, black electrochromic device is obtained；
Described is formula (I) compound to the electrochromic material in electrode thin film layer；
Electrochromic material in described working electrode thin layer is formula (IV) compound；
According to the present invention, present invention working electrode thin layer on TCO glassy layer, obtain being covered with the TCO glass of working electrode thin layer；Concrete, described in be covered with the TCO glass to electrode thin film layer and preferably prepare in accordance with the following methods:
1-1-a) titanium dioxide coating slurry on TCO glass, obtains being attached with the TCO glass of titanium deoxid film；
1-2-a) the TCO glass-impregnated being attached with titanium deoxid film is covered with the TCO glass to electrode thin film layer at the dichloromethane solution containing formula (I) compound。
Wherein, the method for titanium dioxide coating slurry is not had particular/special requirement, painting method well known in the art by the present invention；The concentration of the described dichloromethane solution containing formula (I) compound is preferably 0.05～0.15mol/L, more preferably 0.1～0.12mol/L；
The described TCO glass being covered with working electrode thin layer specifically prepares in accordance with the following methods:
1-1-b) titanium dioxide coating slurry on TCO glass, obtains being attached with the TCO glass of titanium deoxid film；
1-2-b) the TCO glass-impregnated of titanium deoxid film will be attached with it will be covered with at the aqueous solution containing formula (IV) compound the TCO glass of working electrode thin layer。
Wherein, the described solution containing formula (IV) compound is preferably the aqueous solution containing formula (IV) compound, and the concentration of described solution is preferably 0.01～0.06mol/L, more preferably 0.03～0.04mol/L；
According to the present invention, the present invention is also just covered with the TCO glass of working electrode thin layer, dielectric layer, is covered with the TCO glass assemblies to electrode thin film layer, obtains black electrochromic device；The mode assembled is not had particular/special requirement by the present invention, and those skilled in the art can the known general knowledge of this area assemble。
The preparation method of black electrochromic device provided by the invention is simple, and raw material is easy to get, and the performance of the Electrochromic device prepared is good, has broad application prospects, and can be used for the devices such as electrochromic, rearview mirror and color changing display。
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments。Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into the scope of protection of the invention。
Embodiment 1
The synthesis of formula (IV) compound (double; two [((N-phosphono-2-ethyl)-4,4'-bipyridyl)-the methyl]-benzene tetrachloride (PBT) of 1,4-)
Route is:
Preparation method is:
By 4,4'-bipyridyls (6g, 0.04mol), 2-bromoethyl diethyl phosphate (10.0g, 0.045mol), 50ml acetone adds in 150ml round-bottomed flask, loads onto condensing tube, reacts under 45 DEG C of conditions。After reaction a period of time, bottom round-bottomed flask, there is cationic salt precipitates to generate, continue reacting by heating till no longer having precipitation to generate。The precipitation generated is filtered, washs for several times with absolute ether, dry in vacuum drying oven, obtain pure yellow solid, be compound 1。
Take compound 1 (2g, 5mmol), 1,4-dibromo ethyl benzene (0.7g, 2.4mmol), 50ml acetonitrile adds in 100ml round-bottomed flask, load onto condensing tube, return stirring 24h under 70 DEG C of conditions, after reaction terminates, filters the precipitation obtained, with absolute ether and hot acetonitrile wash for several times, vacuum drying oven dries, obtains yellow solid, be compound 2。
Take compound 2 (2g, 1.88mmol), 20% hydrochloric acid solution of 40ml adds in 100ml round-bottomed flask, load onto condensing tube, heated and stirred to back flow reaction overnight, removes solvent, with ethyl alcohol recrystallization under reduced pressure, obtain pure yellow solid after vacuum drying, be the compound (PBT) shown in formula (IV)。
The compound obtained is carried out Structural Identification, and result is shown in Fig. 2～Fig. 3,
Fig. 2 is the compound (PBT) shown in formula (IV) that the embodiment of the present invention 1 prepares1H nuclear magnetic resonance, NMR (1HNMR) spectrogram；As can be seen from Figure 2, its nuclear magnetic data is:1HNMR(300MHz,CDCl3,ppm):δ2.78-2.89(s,6H),3.71-3.75(s,3H),3.94-4.07(d,2H),6.71-6.83(m,4H),6.91-7.00(m,6H),7.15-7.19(m,2H).
Fig. 3 is the Fourier transform infrared spectrogram of the compound (PBT) shown in formula (IV) that the embodiment of the present invention 1 prepares；As can be seen from Figure 3, its FT-IR data are: pyridine ring and proton V on phenyl ring=C-H(3050-3000cm-1), aromatic skeleton vibration performance peak (1600-1450cm-1), C-O-C stretching vibration (1250-1000cm-1), the carbonyl absorption peak (1710-1650cm in phosphoric acid-1), VO-HAt 3200-2500cm-1A broad peak is had in scope。
Embodiment 2
The synthesis of formula (I) compound (4-N, N dimethyl-4 '-methoxyl group-triphenylamine base methylene phosphonic acid (DBP))
Route is:
Preparation method is:
Under inert gas shielding, weigh the bromo-DMA (3.0g of 4-respectively; 15mmol); P-nethoxyaniline (2.2g, 16.8mmol), sodium tert-butoxide (2.0g; 21.0mmol); three (dibenzalacetone) two palladium (0.26g, 0.3mmol), tri-butyl phosphine (0.12g; 0.5mmol) add in 50ml toluene, stirring reaction 24h under 90 DEG C of conditions。After reaction terminates, remove solvent toluene under reduced pressure, dissolve with chloroform。After filtration, with saturated common salt water washing 3 times, collect organic facies, add anhydrous sodium sulfate and dry, be spin-dried for solvent after collecting by filtration organic facies, obtain orange oily liquids by post layer analysis, for compound 1。
Under inert gas shielding; Weigh Compound 1 (2.0g, 8.3mmol), p-bromobenzaldehyde (2.2g; 11.9mmol); three (dibenzalacetone) two palladium (0.15g, 0.16mmol), tri-butyl phosphine (0.07g; 0.33mmol); cesium carbonate (3.60g, 11mmol) adds in 50ml toluene, reacts 24h under 90 DEG C of conditions。After reaction terminates, remove solvent toluene under reduced pressure, dissolve with chloroform。After filtration, with saturated common salt water washing 3 times, collect organic facies, add anhydrous magnesium sulfate and dry, be spin-dried for solvent after collecting by filtration organic facies, obtain orange-yellow oily liquids by post layer analysis, for compound 2。
Weigh Compound 2 (1.8g, 5.20mmol), sodium borohydride (0.26g, 7.26mmol) joins in the round-bottomed flask filling 50ml anhydrous tetrahydro furan, reacts 10h under room temperature condition。After reaction terminates, adding absolute ether and dissolve, with saturated common salt water washing 3 times, collect organic facies, anhydrous magnesium sulfate is dried, and the solution being filtrated to get, removal of solvent under reduced pressure, vacuum drying gilvous viscous liquid, for compound 3。
Under inert gas shielding, Weigh Compound 3 (1.7g, 4.9mmol), zinc bromide (1.10g, 4.9mmol) is dissolved in 5ml NSC 5284, reacts 12h under room temperature condition。Reaction adds a small amount of dilute hydrochloric acid after terminating, and dissolves with dichloromethane, and deionized water extracts 3 times, collects organic facies, filters after drying with anhydrous magnesium sulfate, removes solvent and obtains translucent viscous liquid, for compound 4。
Take compound 4 (1.5g, 3.20mmol) and join in excessive hydrochloric acid weak solution, back flow reaction 12h under 100 DEG C of conditions。Reaction uses chloroform extraction 3 times after terminating, and collects organic facies and also dries with anhydrous magnesium sulfate。The rotary evaporation that reduces pressure after filtration removes solvent, proceeds to vacuum drying oven and dries, obtain translucent liquid, for electrode material (DBP)。
The compound obtained is carried out Structural Identification, and result is shown in Fig. 4～Fig. 5,
Fig. 4 is the compound (DBP) shown in formula (I) that the embodiment of the present invention 2 prepares1H nuclear magnetic resonance, NMR (1HNMR) spectrogram；As can be seen from Figure 4, its nuclear magnetic data is:1HNMR(300MHz,CDCl3,ppm):δ2.78-2.89(s,6H),3.71-3.75(s,3H),3.94-4.07(d,2H),6.71-6.83(m,4H),6.91-7.00(m,6H),7.15-7.19(m,2H).
Fig. 5 is the Fourier transform infrared spectrogram of the compound (DBP) shown in formula (I) that the embodiment of the present invention 2 prepares；As can be seen from Figure 5, its FT-IR data are: pyridine ring and proton V on phenyl ring=C-H(3050-3000cm-1), aromatic skeleton vibration performance peak (1600-1450cm-1), C-O-C stretching vibration (1250-1000cm-1), the carbonyl absorption peak (1710-1650cm in phosphoric acid-1), VO-HAt 3200-2500cm-1A broad peak is had in scope。
Embodiment 3
The preparation of black electrochromic device
Adopt doctor blade method dry under room temperature after titanium dioxide coating nano pulp on FTO glass surface, drying time 15～30min。Dry after completely, under 400-500 DEG C of condition, carry out heat treatment 15-30min, obtain being attached with the FTO glass of titanium deoxid film；
The electrochromic material weighing two kinds of synthesis is configured to PBT/H2The solution of O (0.03M) and DBP/CH2Cl2(0.1M) solution, carries out chemisorbed by the FTO glass-impregnated wherein 24～48h being attached with titanium deoxid film, respectively obtains the TCO glass being covered with working electrode thin layer and is covered with the TCO glass to electrode thin film layer。
Assembling electrochromic device: first sealed membrane (parafilm, 100um) is cut frame shape and is close to working electrode film edge, and stay next injection port；To electrode cap on the working electrode (s, the nano titanium dioxide film to electrode will be made relative with the nano titanium dioxide film thin film of electrochromic electrode, use clamp two plate electrode。With ultra-violet curing glue packaging edge, utilize 1 milliliter of syringe to inject between two plate electrodes by electrolyte by reserved injection port, with ultra-violet curing glue, injection port is sealed again after filling。Black electrochromic device is obtained after assembling。
The structure principle chart of the black electrochromic device obtained is shown in the structure principle chart that Fig. 6, Fig. 6 are black electrochromic device of the present invention；
The performance of the black electrochromic device obtained is detected, and result is shown in Fig. 7～Figure 10:
Fig. 7 is the cyclic voltammetry curve of the device that the embodiment of the present invention prepares, it can be seen that the oxidation-reduction potential of this device respectively 0.5V and-1.5V。
Fig. 8 be the device for preparing of the embodiment of the present invention respectively in coloured state and the transmitance taking off colour killing state；Wherein, block curve represents electrochromic device and fades the transmitance situation of state, and at 570nm place, transmitance reaches 60%。Dashed curve represents its transmitance situation at coloured state, almost all absorbs the light of 400-700nm wavelength in visible region, is black。
Fig. 9 be the coloured state of the device that the embodiment of the present invention prepares and state of fading through rate variance；Wherein, in figure, vertical coordinate represents the transmitance of infrared light, and abscissa represents wavelength, and this curve is deducted coloured state transmitance by state transmitance of fading and obtains, it can be seen that in 570nm place transmitance difference up to 60%。
Figure 10 is the variation diagram that the device that the embodiment of the present invention prepares circulates the coloured state after different number of times and state transmitance of fading continuously, it can be seen that this device cycle 120,000 times, its performance is almost without decay。
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention。It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention。
Claims (10)
1. an electrochromic material, has formula (I) structure,
2. a preparation method for the electrochromic material described in claim 1, including:
It is formula (I) compound by formula (II) converting compounds,
3. preparation method according to claim 2, it is characterised in that the compound of described formula (II) structure prepares in accordance with the following methods:
Formula (III) compound is reacted with p-bromobenzaldehyde, obtains formula (II) compound,
4. a black electrochromic device, including the TCO glassy layer contacted successively, working electrode thin layer, dielectric layer, to electrode thin film layer and TCO glassy layer；
Described is formula (I) compound to the electrochromic material in electrode thin film layer；
Electrochromic material in described working electrode thin layer is formula (IV) compound；
5. Electrochromic device according to claim 4, it is characterised in that the material of described working electrode thin layer is the titanium deoxid film of adsorption-type (IV) compound。
6. Electrochromic device according to claim 4, it is characterised in that the described material to electrode thin film layer is the titanium deoxid film of adsorption-type (I) compound。
7. the Electrochromic device according to claim 5～6 any one, it is characterised in that the TCO glass of described TCO glassy layer is indium tin oxide-coated glass, zinc oxide aluminum electro-conductive glass or fluoride doped indium tin oxide electro-conductive glass。
8. a preparation method for the black electrochromic device described in claim 4～7 any one, including:
1) preparation work electrode thin film layer on TCO glassy layer, obtains being covered with the TCO glass of working electrode thin layer；
Prepared by TCO glassy layer to electrode thin film layer, obtain being covered with the TCO glass to electrode thin film layer；
2) by being covered with the TCO glass of working electrode thin layer, dielectric layer, being covered with the TCO glass assemblies to electrode thin film layer, black electrochromic device is obtained；
Described is formula (I) compound to the electrochromic material in electrode thin film layer；
Electrochromic material in described working electrode thin layer is formula (IV) compound；
9. preparation method according to claim 8, it is characterised in that described in be covered with the TCO glass to electrode thin film layer and specifically prepare in accordance with the following methods:
1-1-a) titanium dioxide coating slurry on TCO glass, obtains being attached with the TCO glass of titanium deoxid film；
1-2-a) by being attached with the TCO glass-impregnated of titanium deoxid film in the dichloromethane solution containing formula (I) compound, obtain being covered with the TCO glass to electrode thin film layer。
10. preparation method according to claim 8, it is characterised in that described in be covered with the TCO glass of working electrode thin layer and specifically prepare in accordance with the following methods:
1-1-b) titanium dioxide coating slurry on TCO glass, obtains scribbling the TCO glass of titanium deoxid film；
1-2-b) by being attached with the TCO glass-impregnated of titanium deoxid film at the aqueous solution containing formula (IV) compound, obtain being covered with the TCO glass of working electrode thin layer。
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