CN105694842B - A kind of electrochromic material and preparation method thereof and black electrochromic material and preparation method thereof - Google Patents
A kind of electrochromic material and preparation method thereof and black electrochromic material and preparation method thereof Download PDFInfo
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- CN105694842B CN105694842B CN201610153786.XA CN201610153786A CN105694842B CN 105694842 B CN105694842 B CN 105694842B CN 201610153786 A CN201610153786 A CN 201610153786A CN 105694842 B CN105694842 B CN 105694842B
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- 239000000463 material Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 150000001875 compounds Chemical class 0.000 claims abstract description 69
- 239000011521 glass Substances 0.000 claims description 60
- 239000010408 film Substances 0.000 claims description 54
- 239000010409 thin film Substances 0.000 claims description 33
- 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 13
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 239000006255 coating slurry Substances 0.000 claims description 7
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 4
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 claims description 3
- 230000000712 assembly Effects 0.000 claims description 2
- 238000000429 assembly Methods 0.000 claims description 2
- 238000003682 fluorination reaction Methods 0.000 claims description 2
- 238000005562 fading Methods 0.000 abstract description 9
- 230000001351 cycling effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000009102 absorption Effects 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- -1 triphenyl amine compound Chemical class 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 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
- 238000001035 drying Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 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
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 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
- 238000004040 coloring Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 238000010438 heat treatment Methods 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
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910001868 water Inorganic materials 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
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 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
- 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
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification 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
- 229920000642 polymer Polymers 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000009738 saturating Methods 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
- 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
- 125000005999 2-bromoethyl group Chemical group 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
- CYIAOJRKGMEQIY-UHFFFAOYSA-N CN(C)c(cc1)ccc1N(c1ccc(CP(O)(O)=O)cc1)c(cc1)ccc1OC Chemical compound CN(C)c(cc1)ccc1N(c1ccc(CP(O)(O)=O)cc1)c(cc1)ccc1OC CYIAOJRKGMEQIY-UHFFFAOYSA-N 0.000 description 1
- APAOIGINBOMEPS-UHFFFAOYSA-N CN(C)c(cc1)ccc1Nc(cc1)ccc1OC Chemical compound CN(C)c(cc1)ccc1Nc(cc1)ccc1OC APAOIGINBOMEPS-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-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
- 150000001768 cations Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000007606 doctor blade method Methods 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
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N methyl phenyl ether Natural products COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 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
- 238000007747 plating 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
- 238000002310 reflectometry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 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
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 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 a kind of 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 electrochromic material to electrode and the compound of formula (IV) structure as working electrode electrochromic material, common assembling obtains electrochromic device, it is black that the device, which realizes coloured state, and colour fading state is faint yellow；And the transmitance difference of the device is high, good cycling stability, can be widely used for the devices such as electrochromic, rearview mirror and color changing display.
Description
Technical field
Off-color material field in field of the present invention, more particularly to a kind of electrochromic material and preparation method thereof and black electricity
Cause off-color material and preparation method thereof.
Background technology
Electrochromism (Electrochromism, EC) refers to optical properties (reflectivity, transmitance, the absorptivity of material
Deng) generation stabilization, the phenomenon of reversible color change in the presence of extra electric field, color and transparency are shown as in appearance
Reversible change.Material with electrochromic property is referred to as electrochromic material, and the device made with electrochromic material claims
For electrochromic device.Electrochromic material is one of focus of material science research in recent years.Electrochromic material is electroluminescent
Important component in Electrochromic device, dominate the electrochromic property of device.According to the structural property of material, electrochromism
Material can be divided into anode electrochromic material (ion insertion coloring) and cathode electrochromic material (ion extracts coloring out).Anode
Electrochromic material can be assembled into complementary type electrochromic device with cathode electrochromic material, and such complementary devices can carry
High overall electrochromic property, such as optical contrast, color change, spectral absorption scope etc..
At present, many seminars have been developed that the electrochromic material and device of multiple color, and black electrochromism material
Material and the problem that device is always that researcher needs to capture.At present, the preparation method of disclosed black electrochromic device
Mainly there are two kinds：One is the black polymer of single working electrode is prepared using the method for chemical copolymerization；The second is utilize two kinds
Polymer above, to obtain black electrochromic device, enables it all to be absorbed in visible region by color addition.
But the unstable chemcial property of the electrochromic material in the black electrochromic device being prepared by the above method,
The optical contrast of device is low, and cyclical stability is poor, and then limits its application in actual production.
The content of the invention
In view of this, the technical problems to be solved by the invention are to provide a kind of electrochromic material and preparation method thereof
And black electrochromic device and preparation method thereof, the property of off-color material in black electrochromic device provided by the invention
It is stable, and transmitance difference is high, good cycling stability.
The invention provides a kind of electrochromic material, has formula (I) structure,
Present invention also offers a kind of preparation method of electrochromic material of the present invention, including：
Formula (II) compound is converted into formula (I) compound,
Preferably, the compound of formula (II) structure is prepared in accordance with the following methods：
Formula (III) compound and p-bromobenzaldehyde are reacted, obtain formula (II) compound,
Present invention also offers a kind of black electrochromic device, including the TCO glassy layers, the working electrode that contact successively are thin
Film layer, dielectric layer, to electrode thin film layer and TCO glassy layers；
The electrochromic material in electrode thin film layer is formula (I) compound；
Electrochromic material in the working electrode film layer is formula (IV) compound；
Preferably, the material of the working electrode film layer is the titanium deoxid film of absorption formula (IV) compound.
Preferably, the material to electrode thin film layer is the titanium deoxid film of absorption formula (I) compound.
Preferably, the TCO glass of the TCO glassy layers is indium tin oxide-coated glass, zinc oxide aluminum electro-conductive glass or fluorine
Change doped indium tin oxide electro-conductive glass.
Present invention also offers a kind of preparation method of black electrochromic device of the present invention, including：
1) the preparation work electrode thin film layer on TCO glassy layers, obtain being covered with the TCO glass of working electrode film layer；
Prepared on TCO glassy layers to electrode thin film layer, obtain being covered with the TCO glass to electrode thin film layer；
2) by the TCO glass for being covered with working electrode film layer, dielectric layer, be covered with TCO glass groups to electrode thin film layer
Dress, obtains black electrochromic device；
The electrochromic material in electrode thin film layer is formula (I) compound；
Electrochromic material in the working electrode film layer is formula (IV) compound；
Preferably, the TCO glass of electrode thin film layer is specifically prepared described be covered with accordance with the following methods：
1-1-a) the titanium dioxide coating slurry on TCO glass, obtain being attached with the TCO glass of titanium deoxid film；
It is 1-2-a) that the TCO glass-impregnateds for being attached with titanium deoxid film is molten in the dichloromethane containing formula (I) compound
In liquid, obtain being covered with the TCO glass to electrode thin film layer.
Preferably, the TCO glass for being covered with working electrode film layer is specifically prepared in accordance with the following methods：
1-1-b) the titanium dioxide coating slurry on TCO glass, obtain being attached with the TCO glass of titanium deoxid film；
The TCO glass-impregnateds of titanium deoxid film will 1-2-b) be attached with the aqueous solution containing formula (IV) compound, obtained
To the TCO glass for being covered with working electrode film layer.
Compared with prior art, the invention provides a kind of triphenyl amine compound electrochromic material and preparation method thereof with
And black electrochromic device and preparation method thereof, electrochromic material provided by the invention have formula (I) structure, and its conduct
The off-color material and the compound of formula (IV) structure as working electrode off-color material of electrode are mutually matched, assembled jointly
To electrochromic device, the coloured state of the device is black, and colour fading state is faint yellow；And the transmitance of the device is high, circulation is steady
It is qualitative good, the devices such as electrochromic, rearview mirror and color changing display are can be widely used for, test result indicates that, the present invention provides
The transmitance difference of black electrochromic device may be up to 60%, and the device cycle 120,000 times, its performance does not almost wane
Subtract.In addition, the preparation method of the black electrochromic device is simple, industrialized production can be achieved.
Brief description of the drawings
Fig. 1 is the structural representation of black electrochromic device of the present invention；
Fig. 2 is the compound (PBT) shown in the formula (IV) that the embodiment of the present invention 1 is prepared1H nuclear magnetic resonance (1HNMR)
Spectrogram；
Fig. 3 is the Fourier transform infrared of the compound (PBT) shown in the formula (IV) that the embodiment of the present invention 1 is prepared
(FT-IR) spectrogram；
Fig. 4 is the compound (DBP) shown in the formula (I) that the embodiment of the present invention 2 is prepared1H nuclear magnetic resonance (1HNMR)
Spectrogram；
Fig. 5 is the Fourier transform infrared of the compound (DBP) shown in the formula (I) that the embodiment of the present invention 2 is prepared
(FT-IR) spectrogram；
Fig. 6 is the structure principle chart of black electrochromic device of the present invention；
Fig. 7 is the cyclic voltammetry curve for the device that the embodiment of the present invention is prepared；
Fig. 8 is the device that is prepared of the embodiment of the present invention respectively in coloured state and the transmitance of colour fading state；
The coloured state for the device that Fig. 9 is prepared for the embodiment of the present invention and the transmitance of colour fading state are poor；
Figure 10 is that the device that is prepared of the embodiment of the present invention continuously circulates the coloured state after different numbers and colour fading state is saturating
Cross the variation diagram of rate.
Embodiment
The invention provides a kind of electrochromic material, has formula (I) structure,
Off-color material provided by the invention with (I) structure, the preparation of black electrochromic device is can be applied to, and made
Standby obtained black electrochromic device can all absorb visible ray in coloured state, and reach complete black.
Present invention also offers the preparation method of electrochromic material shown in a kind of formula (I), including：
Formula (II) compound is converted into formula (I) compound,
According to the present invention, formula (II) compound is converted into formula (I) compound by the present invention, specifically, the preferred tool of the present invention
Body step is：
A) first formula (II) compound and reducing agent are reacted, obtains formula (II-1) compound；
B) formula (II-1) compound and then is again converted into formula (I) compound；
Wherein, the reducing agent in the step a) is preferably sodium borohydride；In the step b), the present invention is preferably by formula
(II-1) compound and zinc bromide and triethyl phosphite react, and obtain the compound containing phosphate, then by phosphate
On ester group hydrolyze in acid condition, obtain formula (I) compound.
Formula (II) compound of the present invention is preferably to react formula (III) compound and p-bromobenzaldehyde, obtains formula
(II) compound, wherein, the catalyst of the reaction is preferably Pd2(dba)3And Cs2CO3。
Formula (III) compound of the present invention is preferably by the way that the bromo- N of 4-, accelerine are mixed with P-nethoxyaniline
Close reaction to be prepared, the catalyst of the reaction is preferably Pd2(dba)3。
Present invention also offers a kind of black electrochromic device, including the TCO glassy layers, the working electrode that contact successively are thin
Film layer, dielectric layer, to electrode thin film layer and TCO glassy layers；
The electrochromic material in electrode thin film layer is formula (I) compound；
Electrochromic material in the working electrode film layer is formula (IV) compound；
In the present invention, TCO (the Transparent Conductive Oxide) glass is to lead in surface of plate glass
The glass for crossing the physically or chemically conductive oxide film that film plating process uniformly plates layer of transparent is referred to as TCO glass.This
In invention, the TCO glass is preferably ITO (indium tin oxide-coated glass), AZO (zinc oxide aluminum electro-conductive glass) or FTO (fluorinations
Doped indium tin oxide electro-conductive glass), more preferably FTO glass.
In the present invention, the material of the working electrode film layer is the titanium deoxid film of absorption formula (IV) compound.This
Compound (double [((N- phosphono -2- ethyls) -4,4'- bipyridyls)-methyl]-four chlorinations of 1,4- of invention to formula (IV) structure
Benzene, be abbreviated as PBT) source there is no a particular/special requirement, those skilled in the art can directly be prepared according to existing report.
The electrolyte of the dielectric layer is preferably the propene carbonate and ethylene carbonate mixed solution of lithium hexafluoro phosphate；
Wherein, the concentration of lithium hexafluoro phosphate is preferably 0.1~0.5mol/L, and the volume ratio of propene carbonate and ethylene carbonate is preferably
1~2: 1.
In the present invention, the material to electrode thin film layer is absorption formula (I) compound (4-N, N dimethyl -4 '-methoxy
Base-triphenylamine base methylene phosphonic acid, is abbreviated as DBP) titanium deoxid film.
Black electrochromic device provided by the invention, by the compound and formula (IV) that select specific formula (I) structure
The compound of structure is respectively as the electrochromic material to electrode and working electrode so that the electrochromic device being prepared
Whole absorptions of visible ray can be realized in coloured state, so that complete black, and the optical contrast of the device is presented in it
Degree is high, i.e., transmitance difference is high, and good cycling stability.In addition, by by the electrochromic material by being chemisorbed on
On titanium deoxid film of the present invention, and then the response time of obtained device is fast, and driving voltage is low.
Specifically, the structural representation of electrochromic device of the present invention is as shown in figure 1, Fig. 1 is of the present invention
The structural representation of black electrochromic device；Its operation principle is as follows：
When switch A is in closure state, and B is in open-circuit condition, electric current is propagated clockwise along wire.Working electrode obtains
To electronics, viologen compound is changed into positive monovalent cation free radical by the positive cationic state of divalence, is changed into from pellucidity
Navy blue state；Now, by redox reaction occurs, also changes from pellucidity due to obtaining the electronics of equivalent for electrode
For yellow green state.And in electrolyte now, due to the electric charge gain and loss of electrode surface, lithium ion and hexafluorophosphoricacid acid ions point
Working electrode is not shifted to and to electrode.Now, device is in colored state.
When device is in colored state, switch B is opened, closure switch A, electric current is just along wire counterclockwise flow.Work
Lose electronics as electrode, the viologen compound in navy blue positive monovalent cation free radical state be oxidized to it is transparent just
Bivalent cation, reduction reaction is occurred to electrode material, yellow green state is taken off to colorless state.Now, device is in transparence
State.
Coloured in this way, just realizing device by being clear to, then by colouring to the conversion of pellucidity.
Present invention also offers a kind of preparation method of black electrochromic device of the present invention, including：
1) the working electrode film layer on TCO glassy layers is prepared, obtains being covered with the TCO glass of working electrode film layer；
Prepare on TCO glassy layers to electrode thin film layer, obtain being covered with the TCO glass to electrode thin film layer；
2) by the TCO glass dielectrics layer for being covered with working electrode film layer, be covered with TCO glass groups to electrode thin film layer
Dress, obtains black electrochromic device；
The electrochromic material in electrode thin film layer is formula (I) compound；
Electrochromic material in the working electrode film layer is formula (IV) compound；
According to the present invention, working electrode film layer of the present invention on TCO glassy layers, obtain being covered with working electrode film layer
TCO glass；Specifically, the TCO glass of electrode thin film layer is preferably prepared described be covered with accordance with the following methods：
1-1-a) the titanium dioxide coating slurry on TCO glass, obtain being attached with the TCO glass of titanium deoxid film；
It is 1-2-a) that the TCO glass-impregnateds for being attached with titanium deoxid film is molten in the dichloromethane containing formula (I) compound
Liquid is covered with the TCO glass to electrode thin film layer.
Wherein, the present invention does not have particular/special requirement, painting method well known in the art to the method for titanium dioxide coating slurry
；The concentration of the dichloromethane solution containing formula (I) compound is preferably 0.05~0.15mol/L, and more preferably 0.1
~0.12mol/L；
The TCO glass for being covered with working electrode film layer is specifically prepared in accordance with the following methods：
1-1-b) the titanium dioxide coating slurry on TCO glass, obtain being attached with the TCO glass of titanium deoxid film；
1-2-b) the TCO glass-impregnateds for being attached with titanium deoxid film are covered with the aqueous solution containing formula (IV) compound
The TCO glass of working electrode film layer.
Wherein, the solution containing formula (IV) compound is preferably the aqueous solution containing formula (IV) compound, described molten
The concentration of liquid is preferably 0.01~0.06mol/L, more preferably 0.03~0.04mol/L；
According to the present invention, the present invention will will also be covered with the TCO glass of working electrode film layer, dielectric layer, be covered with to electricity
The TCO glass assemblies of very thin film layer, obtain black electrochromic device；The present invention does not have particular/special requirement to the mode of assembling, this
Art personnel can be assembled with the common knowledge of this area.
The preparation method of black electrochromic device provided by the invention is simple, and raw material is easy to get, and the discoloration being prepared
The performance of device is good, has broad application prospects, available for devices such as electrochromic, rearview mirror and color changing displays.
It is clearly and completely described below in conjunction with the technical scheme of the embodiment of the present invention, it is clear that described implementation
Example is only part of the embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the common skill in this area
The every other embodiment that art personnel are obtained under the premise of creative work is not made, belong to the model that the present invention protects
Enclose.
Embodiment 1
Formula (IV) compound (double [((N- phosphono -2- ethyls) -4,4'- bipyridyls)-methyl]-benzene tetrachlorides of 1,4-
(PBT) synthesis)
Route is：
Preparation method is：
By 4,4'- bipyridyls (6g, 0.04mol), 2- bromoethyls diethyl phosphate (10.0g, 0.045mol), 50ml acetone
Add in 150ml round-bottomed flasks, load onto condenser pipe, reacted under the conditions of 45 DEG C.After reacting a period of time, round-bottomed flask bottom has
Cationic salt precipitates generate, and continue heating response untill being generated there is no precipitation.The precipitation of generation is filtered, with anhydrous second
Ether washs for several times, is dried in vacuum drying chamber, obtains pure yellow solid, as compound 1.
Compound 1 (2g, 5mmol), Isosorbide-5-Nitrae-dibromo ethyl benzene (0.7g, 2.4mmol) are taken, 50ml acetonitriles add 100ml circles
In the flask of bottom, condenser pipe is loaded onto, the return stirring 24h under the conditions of 70 DEG C, after reaction terminates, obtained precipitation is filtered, with nothing
Water ether and the washing of hot acetonitrile for several times, are dried in vacuum drying chamber, obtain yellow solid, as compound 2.
Compound 2 (2g, 1.88mmol) is taken, 40ml 20% hydrochloric acid solution is added in 100ml round-bottomed flasks, loads onto condensation
Pipe, heating stirring to back flow reaction are stayed overnight, solvent are removed under reduced pressure, with ethyl alcohol recrystallization, gilvous is obtained after vacuum drying
Compound (PBT) shown in solid, as formula (IV).
Structural Identification is carried out to obtained compound, as a result sees Fig. 2~Fig. 3,
Fig. 2 is the compound (PBT) shown in the formula (IV) that the embodiment of the present invention 1 is prepared1H nuclear magnetic resonance (1HNMR)
Spectrogram；As can be seen from Figure 2, its nuclear magnetic data is：1H NMR(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 spectrum of the compound (PBT) shown in the formula (IV) that the embodiment of the present invention 1 is prepared
Figure；As can be seen from Figure 3, its FT-IR data is：Pyridine ring and proton V on phenyl ring=C-H(3050-3000cm-1), aromatic skeleton vibration
Characteristic peak (1600-1450cm-1), C-O-C stretching vibrations (1250-1000cm-1), the carbonyl absorption peak (1710- in phosphoric acid
1650cm-1), VO-HIn 3200-2500cm-1In the range of have a broad peak.
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, the bromo- DMAs of 4- (3.0g, 15mmol) are weighed respectively, to methoxybenzene
Amine (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) is added in 50ml toluene, stirring reaction 24h under the conditions of 90 DEG C.Reaction knot
Shu Hou, solvent toluene is removed under reduced pressure, is dissolved with chloroform.After filtering, with saturated common salt water washing 3 times, collect
Organic phase, anhydrous sodium sulfate drying is added, solvent is spin-dried for after organic phase is collected by filtration, orange oily liquid is obtained by post layer analysis
Body, it is 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) add in 50ml toluene, react 24h under the conditions of 90 DEG C.After reaction terminates, solvent toluene is removed under reduced pressure, is used
Chloroform dissolves.After filtering, with saturated common salt water washing 3 times, organic phase is collected, anhydrous magnesium sulfate is added and dries, filtering
Solvent is spin-dried for after collecting organic phase, orange-yellow oily liquids is obtained by post layer analysis, is compound 2.
Weigh Compound 2 (1.8g, 5.20mmol), sodium borohydride (0.26g, 7.26mmol) are added to that to fill 50ml anhydrous
In the round-bottomed flask of tetrahydrofuran, 10h is reacted under room temperature condition.After reaction terminates, add absolute ether to dissolve, use saturated aqueous common salt
Washing 3 times, organic phase is collected, after anhydrous magnesium sulfate is dried, the solution that is filtrated to get, removal of solvent under reduced pressure is vacuum drying pure
Yellow, viscous liquid, it is compound 3.
Under inert gas shielding, Weigh Compound 3 (1.7g, 4.9mmol), zinc bromide (1.10g, 4.9mmol) dissolving
In 5ml triethyl phosphites, 12h is reacted under room temperature condition.After reaction terminates, a small amount of watery hydrochloric acid is added, uses dichloromethane
Dissolving, deionized water extract 3 times, collect organic phase, are filtered after being dried with anhydrous magnesium sulfate, remove solvent and obtain translucent glue
Thick liquid, it is compound 4.
Compound 4 (1.5g, 3.20mmol) is taken to be added in excessive hydrochloric acid weak solution, back flow reaction under the conditions of 100 DEG C
12h.Reaction uses chloroform extraction 3 times after terminating, and collects organic phase and is simultaneously dried with anhydrous magnesium sulfate.Decompression rotation is steamed after filtering
Hair removes solvent, is transferred to vacuum drying chamber drying, translucent liquid is obtained, for electrode material (DBP).
Structural Identification is carried out to obtained compound, as a result sees Fig. 4~Fig. 5,
Fig. 4 is the compound (DBP) shown in the formula (I) that the embodiment of the present invention 2 is prepared1H nuclear magnetic resonance (1HNMR)
Spectrogram；As can be seen from Figure 4, its nuclear magnetic data is：1H NMR(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 spectrum of the compound (DBP) shown in the formula (I) that the embodiment of the present invention 2 is prepared
Figure；As can be seen from Figure 5, its FT-IR data is：Pyridine ring and proton V on phenyl ring=C-H(3050-3000cm-1), aromatic skeleton vibration
Characteristic peak (1600-1450cm-1), C-O-C stretching vibrations (1250-1000cm-1), the carbonyl absorption peak (1710- in phosphoric acid
1650cm-1), VO-HIn 3200-2500cm-1In the range of have a broad peak.
Embodiment 3
The preparation of black electrochromic device
Dried at room temperature after titanium dioxide coating nano pulp on FTO glass surfaces using doctor blade method, drying time 15
~30min.After drying completely, heat treatment 15-30min is carried out under the conditions of 400-500 DEG C, obtains being attached with titanium deoxid film
FTO glass；
The electrochromic material for weighing two kinds of synthesis is configured to PBT/H2O (0.03M) solution and DBP/CH2Cl2(0.1M)
Solution, will be attached with titanium deoxid film FTO glass-impregnateds wherein 24~48h carry out chemisorbed, respectively obtain and be covered with
The TCO glass of working electrode film layer and it is covered with the TCO glass to electrode thin film layer.
Assembling electrochromic device：Sealed membrane (parafilm, 100um) is first cut into frame shape and is close to working electrode
Film edge, and leave an injection port；Nano titanium dioxide film and electricity to electrode will be made to electrode cap on the working electrode (s
Cause the nano titanium dioxide film film of electrochromic electrode relative, use the plate electrode of clamp two.With uv-curable glue packaging
Edge, between electrolyte is injected into two plate electrodes by reserved injection port using 1 milliliter of syringe, again with ultraviolet solid after filling
Change glue to seal injection port.Black electrochromic device is obtained after assembling.
The structure principle chart of obtained black electrochromic device is shown in that Fig. 6, Fig. 6 are black electrochromism of the present invention
The structure principle chart of device；
The performance of black electrochromic device to obtaining detects, and as a result sees Fig. 7~Figure 10：
Fig. 7 is the cyclic voltammetry curve for the device that the embodiment of the present invention is prepared, it can be seen that the device
Oxidation-reduction potential is respectively 0.5V and -1.5V.
Fig. 8 is the device that the embodiment of the present invention is prepared respectively in coloured state and the transmitance for taking off colour killing state；Wherein,
Block curve represents the transmitance situation of electrochromic device colour fading state, and at 570nm, transmitance reaches 60%.Dashed curve
Its transmitance situation in coloured state is represented, the light of 400-700nm wavelength is absorbed in visible region almost all, it is as black
Color.
The coloured state for the device that Fig. 9 is prepared for the embodiment of the present invention and the transmitance of colour fading state are poor；Wherein, indulged in figure
Coordinate represents the transmitance of infrared light, and abscissa represents wavelength, and this curve subtracts coloured state transmitance by colour fading state transmitance and obtained
Arrive, it can be seen that transmitance difference is up to 60% at 570nm.
Figure 10 is that the device that is prepared of the embodiment of the present invention continuously circulates the coloured state after different numbers and colour fading state is saturating
The variation diagram of rate is crossed, it can be seen that the device cycle 120,000 times, its performance does not almost decay.
The explanation of above example is only intended to help the method and its core concept for understanding the present invention.It should be pointed out that pair
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (7)
1. a kind of black electrochromic device, including the TCO glassy layers, working electrode film layer, dielectric layer, right contacted successively
Electrode thin film layer and TCO glassy layers；
The electrochromic material in electrode thin film layer is formula (I) compound；
Electrochromic material in the working electrode film layer is formula (IV) compound；
2. Electrochromic device according to claim 1, it is characterised in that the material of the working electrode film layer is absorption type
(IV) titanium deoxid film of compound.
3. Electrochromic device according to claim 1, it is characterised in that the material to electrode thin film layer is absorption type
(I) titanium deoxid film of compound.
4. according to the Electrochromic device described in claim 2~3 any one, it is characterised in that the TCO glass of the TCO glassy layers
Glass is indium tin oxide-coated glass, zinc oxide aluminum electro-conductive glass or fluorination doped indium tin oxide electro-conductive glass.
5. a kind of preparation method of the black electrochromic device described in claim 1, including：
1) the preparation work electrode thin film layer on TCO glassy layers, obtain being covered with the TCO glass of working electrode film layer；
Prepared on TCO glassy layers to electrode thin film layer, obtain being covered with the TCO glass to electrode thin film layer；
2) by the TCO glass for being covered with working electrode film layer, dielectric layer, be covered with TCO glass assemblies to electrode thin film layer, obtain
To black electrochromic device；
The electrochromic material in electrode thin film layer is formula (I) compound；
Electrochromic material in the working electrode film layer is formula (IV) compound；
6. preparation method according to claim 5, it is characterised in that the TCO glass tool being covered with to electrode thin film layer
Body is prepared in accordance with the following methods：
1-1-a) the titanium dioxide coating slurry on TCO glass, obtain being attached with the TCO glass of titanium deoxid film；
The TCO glass-impregnateds of titanium deoxid film will 1-2-a) be attached with the dichloromethane solution containing formula (I) compound,
Obtain being covered with the TCO glass to electrode thin film layer.
7. preparation method according to claim 5, it is characterised in that the TCO glass for being covered with working electrode film layer
Specifically it is prepared in accordance with the following methods：
1-1-b) the titanium dioxide coating slurry on TCO glass, obtain scribbling the TCO glass of titanium deoxid film；
The TCO glass-impregnateds of titanium deoxid film will 1-2-b) be attached with the aqueous solution containing formula (IV) compound, covered
There is the TCO glass of working electrode film layer.
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