CN102250484A - Carbazolyl organic dye used for dye-sensitized solar cells and preparation method thereof - Google Patents
Carbazolyl organic dye used for dye-sensitized solar cells and preparation method thereof Download PDFInfo
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- CN102250484A CN102250484A CN201110131131XA CN201110131131A CN102250484A CN 102250484 A CN102250484 A CN 102250484A CN 201110131131X A CN201110131131X A CN 201110131131XA CN 201110131131 A CN201110131131 A CN 201110131131A CN 102250484 A CN102250484 A CN 102250484A
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- organic dye
- carbazyl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 title abstract description 5
- 239000000975 dye Substances 0.000 claims abstract description 107
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000000746 purification Methods 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 51
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 37
- 206010070834 Sensitisation Diseases 0.000 claims description 30
- 230000008313 sensitization Effects 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 16
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 16
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 8
- 239000005695 Ammonium acetate Substances 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 229940043376 ammonium acetate Drugs 0.000 claims description 8
- 235000019257 ammonium acetate Nutrition 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- 239000012362 glacial acetic acid Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 7
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical class CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 claims description 7
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- 239000008151 electrolyte solution Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium(II) oxide Chemical compound [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- IYVYLVCVXXCYRI-UHFFFAOYSA-N 1-propylimidazole Chemical class CCCN1C=CN=C1 IYVYLVCVXXCYRI-UHFFFAOYSA-N 0.000 claims description 3
- YSHMQTRICHYLGF-UHFFFAOYSA-N 4-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=NC=C1 YSHMQTRICHYLGF-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000010335 hydrothermal treatment Methods 0.000 claims description 3
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 125000002346 iodo group Chemical group I* 0.000 claims description 3
- 238000004080 punching Methods 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- 229920001169 thermoplastic Polymers 0.000 claims description 3
- 239000004416 thermosoftening plastic Substances 0.000 claims description 3
- -1 4Be hydrogen Chemical class 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 210000005252 bulbus oculi Anatomy 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 230000006798 recombination Effects 0.000 abstract description 5
- 238000005215 recombination Methods 0.000 abstract description 5
- 125000003118 aryl group Chemical group 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 210000004027 cell Anatomy 0.000 abstract 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 210000004940 nucleus Anatomy 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 238000001228 spectrum Methods 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000001235 sensitizing effect Effects 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 238000012856 packing Methods 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 230000005764 inhibitory process Effects 0.000 description 3
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 2
- KAFZOLYKKCWUBI-HPMAGDRPSA-N (2s)-2-[[(2s)-2-[[(2s)-1-[(2s)-3-amino-2-[[(2s)-2-[[(2s)-2-(3-cyclohexylpropanoylamino)-4-methylpentanoyl]amino]-5-methylhexanoyl]amino]propanoyl]pyrrolidine-2-carbonyl]amino]-5-(diaminomethylideneamino)pentanoyl]amino]butanediamide Chemical compound N([C@@H](CC(C)C)C(=O)N[C@@H](CCC(C)C)C(=O)N[C@@H](CN)C(=O)N1[C@@H](CCC1)C(=O)N[C@@H](CCCN=C(N)N)C(=O)N[C@@H](CC(N)=O)C(N)=O)C(=O)CCC1CCCCC1 KAFZOLYKKCWUBI-HPMAGDRPSA-N 0.000 description 2
- PNHBRYIAJCYNDA-VQCQRNETSA-N (4r)-6-[2-[2-ethyl-4-(4-fluorophenyl)-6-phenylpyridin-3-yl]ethyl]-4-hydroxyoxan-2-one Chemical compound C([C@H](O)C1)C(=O)OC1CCC=1C(CC)=NC(C=2C=CC=CC=2)=CC=1C1=CC=C(F)C=C1 PNHBRYIAJCYNDA-VQCQRNETSA-N 0.000 description 2
- PSWDQTMAUUQILQ-UHFFFAOYSA-N 2-[(6-methoxy-4-methylquinazolin-2-yl)amino]-5,6-dimethyl-1h-pyrimidin-4-one Chemical compound N1=C(C)C2=CC(OC)=CC=C2N=C1NC1=NC(=O)C(C)=C(C)N1 PSWDQTMAUUQILQ-UHFFFAOYSA-N 0.000 description 2
- IJVRPNIWWODHHA-UHFFFAOYSA-N 2-cyanoprop-2-enoic acid Chemical compound OC(=O)C(=C)C#N IJVRPNIWWODHHA-UHFFFAOYSA-N 0.000 description 2
- OVDGUTHABMXVMI-UHFFFAOYSA-N 3-nitro-4-(propylamino)benzoic acid Chemical compound CCCNC1=CC=C(C(O)=O)C=C1[N+]([O-])=O OVDGUTHABMXVMI-UHFFFAOYSA-N 0.000 description 2
- HIHOEGPXVVKJPP-JTQLQIEISA-N 5-fluoro-2-[[(1s)-1-(5-fluoropyridin-2-yl)ethyl]amino]-6-[(5-methyl-1h-pyrazol-3-yl)amino]pyridine-3-carbonitrile Chemical compound N([C@@H](C)C=1N=CC(F)=CC=1)C(C(=CC=1F)C#N)=NC=1NC=1C=C(C)NN=1 HIHOEGPXVVKJPP-JTQLQIEISA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- TZYWCYJVHRLUCT-VABKMULXSA-N N-benzyloxycarbonyl-L-leucyl-L-leucyl-L-leucinal Chemical compound CC(C)C[C@@H](C=O)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(C)C)NC(=O)OCC1=CC=CC=C1 TZYWCYJVHRLUCT-VABKMULXSA-N 0.000 description 2
- SRVFFFJZQVENJC-IHRRRGAJSA-N aloxistatin Chemical compound CCOC(=O)[C@H]1O[C@@H]1C(=O)N[C@@H](CC(C)C)C(=O)NCCC(C)C SRVFFFJZQVENJC-IHRRRGAJSA-N 0.000 description 2
- OSVHLUXLWQLPIY-KBAYOESNSA-N butyl 2-[(6aR,9R,10aR)-1-hydroxy-9-(hydroxymethyl)-6,6-dimethyl-6a,7,8,9,10,10a-hexahydrobenzo[c]chromen-3-yl]-2-methylpropanoate Chemical compound C(CCC)OC(C(C)(C)C1=CC(=C2[C@H]3[C@H](C(OC2=C1)(C)C)CC[C@H](C3)CO)O)=O OSVHLUXLWQLPIY-KBAYOESNSA-N 0.000 description 2
- 229940125796 compound 3d Drugs 0.000 description 2
- 229940125872 compound 4d Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QAPTWHXHEYAIKG-RCOXNQKVSA-N n-[(1r,2s,5r)-5-(tert-butylamino)-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](NC(C)(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 QAPTWHXHEYAIKG-RCOXNQKVSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- RWWYLEGWBNMMLJ-YSOARWBDSA-N remdesivir Chemical compound NC1=NC=NN2C1=CC=C2[C@]1([C@@H]([C@@H]([C@H](O1)CO[P@](=O)(OC1=CC=CC=C1)N[C@H](C(=O)OCC(CC)CC)C)O)O)C#N RWWYLEGWBNMMLJ-YSOARWBDSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 1
- KUBSCXXKQGDPPD-UHFFFAOYSA-N 3-bromo-9-phenylcarbazole Chemical compound C12=CC=CC=C2C2=CC(Br)=CC=C2N1C1=CC=CC=C1 KUBSCXXKQGDPPD-UHFFFAOYSA-N 0.000 description 1
- KIHPDGGDZZCYBT-UHFFFAOYSA-N CC1C=CC=C(C)C1 Chemical compound CC1C=CC=C(C)C1 KIHPDGGDZZCYBT-UHFFFAOYSA-N 0.000 description 1
- 101100030361 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pph-3 gene Proteins 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Hybrid Cells (AREA)
Abstract
The invention relates to a pure organic dye which adopts a carbazole group as the electron donor and is used for dye-sensitized solar cells and a preparation method thereof. With a molecular structure of D-Pi-A and a good light-capturing capacity, the dye has an adsorption spectrum and a fluorescence spectrum that are adjustable by aromatic nucleuses of different kinds and numbers. Belonging to pure organic dyes, the dye of the invention, compared with ruthenium dyes, has simple-structured and cheap raw materials that are in abundant supply and easy for purification, thus having the advantages of low cost and simple production, etc. In addition, the dye of the invention can effectively improve the electron lifetime and the open circuit photovoltage, and can obtain energy conversion efficiency over 5%. Compared with dyes without a long alkyl chain side group, the dye provided in the invention can inhibit the charge recombination degree to less than one-tenth of the original, thus boasting good development and application prospects in the field of dye-sensitized solar cells.
Description
Technical field
The present invention relates to the organic photoelectrical material field, relate to particularly that a kind of to be used for the novel of dye sensitization solar battery be that electron donor, aromatic nucleus are the bridge chain and connect pure organic dye of carbazyl of alpha-cyanoacrylate and preparation method thereof with the carbazole group.
Background technology
Along with shortage of resources and problem of environmental pollution become increasingly conspicuous, people day by day strengthen the care of energy problem, sun power is the desirable energy of human long-term survival as a kind of renewable and clean energy resource, taught in 1991 dye sensitization solar battery (the Dye-sensitized solar cells that at first proposes by Switzerland M. Gr tzel, DSSC) as a kind of novel solar battery, for the mankind provide at a low price, efficiently, green regenerative energy sources is brought hope, this battery is based on the development of plant chlorophyll photosynthesis principle and goes out, battery structure is simple, mainly by working electrode, electrolytic solution and counter electrode are formed.Working electrode is by sintering one deck nano porous titanium dioxide film in the conductive glass substrate, and adsorbs one deck light-sensitive coloring agent in the above and make; Electrolytic solution can be liquid, also can be accurate solid-state and solid-state, the most frequently used I
3 -/ I
-Redox couple; Counter electrode generally is the conductive glass that is coated with one deck platinum.
Important component part as battery, the photosensitizers dyestuff can absorb sunlight effectively, and produce excitation electron thus, be injected into then in the semi-conductive conduction bands such as titanium dioxide, so the photoelectric properties of dyestuff have fundamental influence to the photoelectric transformation efficiency of dye sensitization solar battery.At present, the best dye sensitizing agent of performance is the title complex that contains noble ruthenium, and wherein the most classical is N3 and black dyestuff, yet expensive precious metal price and rare precious metal resource make its extensive industrialization be subjected to very big restriction.Meanwhile, pure organic dye more and more is subject to people's attention owing to having advantages such as with low cost, high molar absorptivity and structure easy-regulating, and become the research focus in this field, and be electron donor with the carbazole group, aromatic nucleus is bridge chain and the pure organic dye of carbazyl that connects an alpha-cyanoacrylate report not also at present.
Summary of the invention
It is the pure organic dye and preparation method thereof of electron donor with the carbazole group that the technical problem to be solved in the present invention provides a kind of, this dyestuff is applied to dye sensitization solar battery, the electron lifetime and the open circuit photovoltage of battery can be effectively improved, and 5% effciency of energy transfer can be obtained to surpass.
For solving the problems of the technologies described above, the technical solution used in the present invention is: carbazyl organic dye of the present invention has following general structure:
In the formula, R
1~ R
4Be hydrogen, alkyl or aralkyl, n is 1 ~ 4 integer.
As limitation of the invention further, carbazyl organic dye of the present invention is any one among the structural formula 1-6:
Structural formula 1:
Structural formula 2:
Structural formula 3:
Structural formula 4:
Structural formula 5:
，
Structural formula 6:
In addition, the synthetic route of carbazyl organic dye of the present invention is as follows:
The synthetic method of this organic dye is carried out according to following steps:
(1) compound b is synthetic: under nitrogen protection, a certain amount of compound a is dissolved in the tetrahydrofuran (THF) (THF) fully, reaction system places-20 ° below the C, slowly splash into 0.9 ~ 2 times the n-Butyl Lithium that molar weight is a compound a with syringe, after low temperature reacts 0.1 ~ 2 h down, splashing into molar weight again is 1.1 ~ 2.5 times of tributyltin chlorides of compound a, after dropwising reaction system is warming up to room temperature, stir 2 ~ 36 h, reaction stops with ammonium chloride solution, uses dichloromethane extraction then, deionized water wash, use anhydrous sodium sulfate drying again, eliminate solvent and get compound b, be not further purified processing and be directly used in next step reaction;
(2) compound d is synthetic: under nitrogen protection, and with compound b, c and Pd (PPh
3)
4According to mol ratio is that the ratio of 1.1 ~ 2:1:0.005 ~ 0.2 is dissolved in N, in the dinethylformamide (DMF), more than the 80 ° of above reaction of C 4 h, eliminates solvent, and post separates to purify and obtains compound d;
(3) dyestuff e's is synthetic: with compound d, cyanoacetic acid and ammonium acetate are that the ratio of 1:1 ~ 2.5:0.05 ~ 0.5 is dissolved in the Glacial acetic acid according to mol ratio, more than refluxed under nitrogen 4 h, the methylene dichloride dilution, deionized water repeatedly washs, use anhydrous sodium sulfate drying again, eliminate solvent, post separates purification and obtains described carbazyl organic dye e.
In addition, carbazyl organic dye of the present invention is applied in the dye sensitization solar battery, this dye sensitization solar battery prepares through following steps:
(1) conductive glass pre-treatment: the FTO conductive glass is cut into 1.5 * 1.5 cm sizes, in acetone, ethanol and deionized water, fully clean successively, and dry up with nitrogen gas stream with ultrasonic wave;
(2) preparation of titania slurry: dropwise be added drop-wise to the different third oxygen titanium in the deionized water, and at ambient temperature more than stirring reaction 1 h, fully generate white precipitate, white precipitate is filtered, obtain titanium dioxide precipitation, this precipitation is transferred in the round bottom reaction flask, slowly drip the tetramethylammonium hydroxide aqueous solution of equivalent, add the deionized water constant volume again, powerful stirring reaction 1 ~ 5 h in 100 ~ 150 ° of C oil baths, naturally cool to room temperature, the white colloid that obtains after reaction finished is transferred in the autoclave and constant volume, hydrothermal treatment consists 6 ~ 24 h under the condition of 150 ~ 300 ° of C take out behind the naturally cooling and carry out supersound process, obtain milky TiO 2 sol;
(3) preparation of dye solution: described carbazyl organic dye is dissolved in the dry toluene, is mixed with the solution of 0.3 mmol/L;
(4) electrolytical preparation: contain 0.1 mol/L lithium iodide, 0.05 mol/L iodine, 0.6 mol/L iodo 1,2-dimethyl, the different eyeball solution of 3-n-propyl imidazoles and 0.5 mol/L 4-tert .-butylpyridine with the anhydrous acetonitrile preparation;
(5) preparation of working electrode: the resulting titania slurry of step (2) is formed one deck sol pellicle by rotation film forming, silk screen printing or pulling film forming method on clean conductive glass, dried film is put into retort furnace, temperature slowly is warming up to 450 ~ 550 ° of C, constant temperature 0.5 ~ 10 h, naturally cool to room temperature, with gained TiO
2Electrode directly immerses in the dye solution of step (3) gained and keeps 24 h;
(6) preparation of counter electrode: with the aqueous isopropanol of 0.1 ~ 50 mmol/L Platinic chloride be coated in equably clean in the step (1) and punching after conductive glass surface, place then in the retort furnace in 400 ~ 500 ° of C roasting 30 min, be cooled to room temperature and place in the moisture eliminator standby;
(7) cell package: with nitrogen gas stream with the absorption of step (5) gained the TiO of carbazyl organic dye
2The platinum counter electrode of working electrode and step (6) gained blows clean, and it is two electrodes are staggered relatively, conducting surface inwardly, thermoplastic film is inserted at the edge, heats 5 ~ 30 s under 100 ~ 120 ° of C conditions and solidifies, and the used for electrolyte syringe of step (4) the gained aperture by counter electrode is injected in the battery, and utilize wicking action to make to be full of electrolytic solution in the cavity of two electrodes, after treating the interior no bubble of two electrodes, aperture is sealed, promptly made described dye sensitization solar battery with seal gum.
Carbazyl dyestuff of the present invention has D-π-A molecular structure, has good light capture ability, its absorption spectrum and fluorescence spectrum can be regulated by the aromatic nucleus of different sorts and number, belong to pure organic dye, compare with ruthenium class dyestuff, its raw material mix is simple, cheap and easy to get, and in liberal supply, be easy to purifying, therefore have with low costly, produce advantages such as easy.In addition, carbazole and derivative thereof have excellent photoelectric performance, as cavity transmission ability and the sub-ability of strong power supply, it is the good photoelectric material of a class, this class organic dye is applied in the dye sensitization solar battery, can improve the life-span and the open circuit photovoltage of electronics effectively, and can obtain to surpass 5% energy conversion efficiency, in addition, compare with the dyestuff that does not comprise the long alkyl chain side group, such dyestuff can be suppressed to the charge recombination degree original below 1/10th, so such dyestuff has excellent development and application prospect in field of dye-sensitized solar cells.
Embodiment
The present invention is further detailed explanation below in conjunction with drawings and Examples.
Embodiment 1:Synthesizing of dyestuff 1
Synthetic route is as follows:
(1) compound 1b's is synthetic:
Under nitrogen protection; 0.63 g (1.63 mmol) 1a is dissolved among the 20 mL THF; reaction system places-78 ° of C; slowly splash into 1.2 mL (1.96 mmol) n-Butyl Lithiums (1.6 mol/L) with syringe; after reacting 1 h; splash into 0.6 mL (2.21 mmol) tributyltin chloride again; after dropwising reaction system is warming up to room temperature, stirs 12 h, reaction is with 10% the ammonium chloride solution quencher of 100 mL; use dichloromethane extraction then; deionized water wash is used anhydrous sodium sulfate drying again, eliminates solvent and gets 0.94 g compound 1b; yield 97% is not further purified processing and is directly used in next step reaction.
(2) compound 1d's is synthetic:
Under nitrogen protection; with 0.94 g (1.58 mmol) 1b, (preparation of compound 1c is referring to document R. Chen et al., Chem. Mater. 2007 for 0.43g (1.58 mmol) 1c; 19,4007) and 91 mg (0.08 mmol) Pd (PPh
3)
4Be dissolved among the 40 mL DMF, 90 ° of C react 10 h, eliminate solvent, and post separates purification and obtains 0.50 g compound 1d, yield 63%.
(3) dyestuff 1 is synthetic:
With 450 mg (0.90 mmol) 1d, 115 mg (1.35 mmol) cyanoacetic acid and 21 mg (0.27 mmol) ammonium acetate are dissolved in the 60 mL Glacial acetic acid, refluxed under nitrogen 7 h, the methylene dichloride dilution, deionized water repeatedly washs, and uses anhydrous sodium sulfate drying again, eliminates solvent, post separates purification and obtains 260 mg dyestuffs 1, yield 51%.
Embodiment 2:Synthesizing of dyestuff 2
Synthetic route is as follows:
(1) compound 2b's is synthetic:
Under nitrogen protection; 0.54 g (1.57 mmol) 2a is dissolved among the 40 mL THF; reaction system places-78 ° of C; slowly splash into 1.1 mL (1.73 mmol) with syringe) n-Butyl Lithium (1.6mol/L); after reacting 2 h; splash into 0.5 mL(2.04 mmol again) tributyltin chloride; after dropwising reaction system is warming up to room temperature, stirs 12 h, reaction is with 10% the ammonium chloride solution quencher of 100 mL; use dichloromethane extraction then; deionized water wash is used anhydrous sodium sulfate drying again, eliminates solvent and gets 0.81 g compound 2b; yield 93% is not further purified processing and is directly used in next step reaction.
(2) compound 2d's is synthetic:
Under nitrogen protection, with 0.81 g (1.46 mmol) 2b, 0.64 g (1.46 mmol) 2c and 84 mg (0.073 mmol) Pd (PPh
3)
4Be dissolved among the 40 mL DMF, 85 ° of C react 8 h, eliminate solvent, and post separates purification and obtains 466 mg compound 2d, yield 51%.
(3) dyestuff 2 is synthetic:
With 435 mg (0.69 mmol) 2d, 89 mg (1.04 mmol) cyanoacetic acid and 16 mg (0.21 mmol) ammonium acetate are dissolved in the 60 mL Glacial acetic acid, refluxed under nitrogen 6h, the methylene dichloride dilution, deionized water repeatedly washs, and uses anhydrous sodium sulfate drying again, eliminates solvent, post separates purification and obtains 220 mg dyestuffs 2, yield 46%.
Embodiment 3:Synthesizing of dyestuff 3
Synthetic route is as follows:
(1) compound 3b's is synthetic:
Under nitrogen protection; with 3a; be that (synthetic method is seen document S. O. Jeon et al. to 3-bromo-9-phenyl-carbazole; Adv. Funct. Mater. 2009; 19; 3644.) 253 mg (0.79 mmol) are dissolved among the 30 mL THF; reaction system places-78 ° of C, slowly splashes into 0.5 mL (1.73 mmol) n-Butyl Lithium (1.6 mol/L) with syringe, react 2 h after; splash into 0.25 mL(1.03 mmol again) tributyltin chloride; after drip finishing reaction system is warming up to room temperature, stirs 12 h, reaction is with 10% the ammonium chloride solution quencher of 100 mL; use dichloromethane extraction then; deionized water wash is used anhydrous sodium sulfate drying again, eliminates solvent and gets 412 mg compound 3b; yield 98% is not further purified processing and is directly used in next step reaction.
(2) compound 3d's is synthetic:
Under nitrogen protection, with 412 mg (0.78 mmol) 3b, 484 mg (0.70 mmol) 3c and 45 mg (0.039 mmol) Pd (PPh
3)
4Be dissolved among the 40 mL DMF, 80 ° of C reaction 9h eliminate solvent, and post separates purification and obtains 317 mg compound 3d, yield 53%.
(3) dyestuff 3 is synthetic:
With 294 mg (0.34 mmol) 3d, 44 mg (0.52 mmol) cyanoacetic acid and 8 mg (0.10 mmol) ammonium acetate are dissolved in the 20 mL Glacial acetic acid, refluxed under nitrogen 6 h, the methylene dichloride dilution, deionized water repeatedly washs, and uses anhydrous sodium sulfate drying again, eliminates solvent, post separates purification and obtains 119 mg dyestuffs 3, yield 38%.
Embodiment 4:Synthesizing of dyestuff 4
Synthetic route is as follows:
(1) compound 4b's is synthetic:
Under nitrogen protection; 275 mg (1.06 mmol) 4a is dissolved among the 40 mL THF; reaction system places-78 ° of C; slowly splash into 0.7 mL (1.17 mmol) n-Butyl Lithium (1.6mol/L) with syringe; after reacting 2 h; splash into 0.33 mL (1.38 mmol) tributyltin chloride again; after drip finishing reaction system is warming up to room temperature, stirs 12 h, reaction is with 10% the ammonium chloride solution quencher of 100 mL; use dichloromethane extraction then; deionized water wash is used anhydrous sodium sulfate drying again, eliminates solvent and gets 489 mg compound 4b; yield 98% is not further purified processing and is directly used in next step reaction.
(2) compound 4d's is synthetic:
Under nitrogen protection, with 489 mg (1.04 mmol) 4b, 517 mg (1.04 mmol) 4c and 60 mg (0.052 mmol) Pd (PPh3) 4 are dissolved among the 40 mL DMF; 85 ° of C react 8 h; eliminate solvent, post separates purification and obtains 292 mg compound 4d, yield 47%.
(3) dyestuff 4 is synthetic:
With 278 mg (0.46 mmol) 4d, 59 mg (0.69 mmol) cyanoacetic acid and 11 mg (0.14 mmol) ammonium acetate are dissolved in the 40 mL Glacial acetic acid, refluxed under nitrogen 6 h, the methylene dichloride dilution, deionized water repeatedly washs, and uses anhydrous sodium sulfate drying again, eliminates solvent, post separates purification and obtains 150 mg dyestuffs 4, yield 49%.
Embodiment 5:Synthesizing of dyestuff 5
Synthetic route is as follows:
(1) compound 5b's is synthetic:
Under nitrogen protection; 53 mg (0.19 mmol) 5a is dissolved among the 20 mL THF; reaction system places-78 ° of C; slowly splash into 0.13 mL (1.17 mmol) n-Butyl Lithium (1.6 mol/L) with syringe; after reacting 2 h; splash into 0.07 mL (0.24 mmol) tributyltin chloride again; after dropwising reaction system is warming up to room temperature, keeps 12 h, reaction is with 10% the ammonium chloride solution quencher of 100 mL; use dichloromethane extraction then; deionized water wash is used anhydrous sodium sulfate drying again, eliminates solvent and gets 87 mg compound 5b; yield 95% is not further purified processing and is directly used in next step reaction.
(2) compound 5c's is synthetic:
Under nitrogen protection, with 87 mg(0.18 mmol) 5b, 137 mg (0.20 mmol) 3c and 21 mg (0.018 mmol) Pd (PPh
3)
4Be dissolved among the 20 mL DMF, the 80 ° of above reaction of C 8 h eliminate solvent, and post separates purification and obtains 89 mg compound 5c, yield 60%.
(3) dyestuff 5 is synthetic:
With 77 mg (0.095 mmol) 5c, 12 mg (0.14 mmol) cyanoacetic acid and 2 mg(0.029 mmol) ammonium acetate is dissolved in the 40 mL Glacial acetic acid, refluxed under nitrogen 6 h, the methylene dichloride dilution, deionized water repeatedly washs, and uses anhydrous sodium sulfate drying again, eliminates solvent, post separates purification and obtains 57 mg dyestuffs 5, yield 69%.
Embodiment 6:Synthesizing of dyestuff 6
Synthetic route is as follows:
(1) compound 6b's is synthetic:
Under nitrogen protection, with 271 mg (0.31 mmol) 6a, 300 mg (0.62 mmol) 5b and 50 mg(0.043 mmol) Pd (PPh
3)
4Be dissolved among the 20 mL DMF, the 80 ° of above reaction of C 8 h eliminate solvent, and post separates purification and obtains 236 mg compound 6b, yield 77%.
(2) dyestuff 6 is synthetic:
With 218 mg (0.22 mmol) 6b, 28 mg (0.33 mmol) cyanoacetic acid and 5 mg (0.066 mmol) ammonium acetate are dissolved in the 40 mL Glacial acetic acid, refluxed under nitrogen 6 h, the methylene dichloride dilution, deionized water repeatedly washs, and uses anhydrous sodium sulfate drying again, eliminates solvent, post separates purification and obtains 171 mg dyestuffs 6, yield 73%.
Embodiment 7:With dyestuff 1 is the preparation of the dye sensitization solar battery of sensitizing agent
The FTO conductive glass is cut into 1.5 * 1.5 cm sizes, in acetone, ethanol and deionized water, fully clean successively with ultrasonic wave, and dry up with nitrogen gas stream, the different third oxygen titanium dropwise is added drop-wise in the deionized water, and at ambient temperature more than stirring reaction 1 h, fully generate white precipitate, white precipitate is filtered, obtain titanium dioxide precipitation, this precipitation is transferred in the round bottom reaction flask, slowly drip the tetramethylammonium hydroxide aqueous solution of equivalent, add the deionized water constant volume again.Powerful stirring reaction 2 h naturally cool to room temperature in 140 ° of C oil baths, and the white colloid that obtains after reaction is finished is transferred in the autoclave and constant volume, hydrothermal treatment consists 12 h under the condition of 220 ° of C.Take out behind the naturally cooling and carry out supersound process, obtain milky TiO 2 sol.On clean conductive glass, form one deck sol pellicle by the silk screen printing film.Dried film is put into retort furnace, and temperature slowly is warming up to 500 ° of C, constant temperature half an hour naturally cools to room temperature, promptly obtains TiO
2Working electrode is with gained TiO
2 workElectrode directly immerses the anhydrous toluene solution (0.3 mmol/L) of dyestuff 1.
With the aqueous isopropanol of 0.1 ~ 50m mol/L Platinic chloride be coated in equably clean in the step (1) and punching after conductive glass surface, place then in the retort furnace in 400 ~ 500 ° of C roasting 30 min, be cooled to room temperature and obtain the platinum counter electrode, be positioned in the moisture eliminator standby
Above-mentioned working electrode that obtains and platinum counter electrode are blown clean, and two electrodes are staggered relatively, conducting surface inwardly, thermoplastic film is inserted at the edge, put into after fixing 110 ° of C down heating 10 s solidify.With 0.1 mol/L lithium iodide, 0.05 mol/L iodine, 0.6 mol/L iodo 1, the 2-dimethyl, the acetonitrile solution of 3-n-propyl imidazoles and 0.5 mol/L 4-tert .-butylpyridine is injected in the battery by the aperture of counter electrode, and utilizes wicking action to make to be full of electrolytic solution in the cavity of two electrodes, after treating the interior no bubble of two electrodes, with seal gum aperture is sealed, prepared dye sensitization solar battery, wherein cell area is 0.2304 cm
2Record the current-voltage curve of dye sensitization solar battery under the AM1.5 simulated solar irradiation, the photovoltage (Voc) that obtains opening a way is 0.72 V, and short-circuit photocurrent (Jsc) is 6.32 mA/cm
2, packing factor (FF) is 75%, effciency of energy transfer (η) is 3.4%.
Embodiment 8:With dyestuff 2 is the preparation of the dye sensitization solar battery of sensitizing agent
Dyestuff 2 is dissolved in the dry toluene, be made into the solution of 0.3 mmol/L, according to the assembling of process shown in the embodiment 7 dye sensitization solar battery, under the AM1.5 simulated solar irradiation, record the current-voltage curve of dye sensitization solar battery, the photovoltage (Voc) that obtains opening a way is 0.75 V, and short-circuit photocurrent (Jsc) is 6.97 mA/cm
2, packing factor (FF) is 71%, effciency of energy transfer (η) is 3.7%.
Embodiment 9:With dyestuff 3 is the preparation of the dye sensitization solar battery of sensitizing agent
Dyestuff 3 is dissolved in the dry toluene, be made into the solution of 0.3 mmol/L, according to the assembling of process shown in the embodiment 7 dye sensitization solar battery, under the AM1.5 simulated solar irradiation, record the current-voltage curve of dye sensitization solar battery, the photovoltage (Voc) that obtains opening a way is 0.77 V, and short-circuit photocurrent (Jsc) is 8.22 mA/cm
2, packing factor (FF) is 73%, effciency of energy transfer (η) is 4.6%.
Embodiment 10:With dyestuff 4 is the preparation of the dye sensitization solar battery of sensitizing agent
Dyestuff 4 is dissolved in the dry toluene, be made into the solution of 0.3 mmol/L, according to the assembling of process shown in the embodiment 7 dye sensitization solar battery, under the AM1.5 simulated solar irradiation, record the current-voltage curve of dye sensitization solar battery, the photovoltage (Voc) that obtains opening a way is 0.79 V, and short-circuit photocurrent (Jsc) is 7.71 mA/cm
2, packing factor (FF) is 75%, effciency of energy transfer (η) is 4.6%.In addition, analyze by the intensity modulation electrochemical impedance, electric charge inhibition degree is lower than 1/10th of charge recombination degree in the battery of the similar dyestuff assembling that does not contain side group in this battery.
Embodiment 11:With dyestuff 5 is the preparation of the dye sensitization solar battery of sensitizing agent
Dyestuff 5 is dissolved in the dry toluene, be made into the solution of 0.3 mmol/L, according to the assembling of process shown in the embodiment 7 dye sensitization solar battery, under the AM1.5 simulated solar irradiation, record the current-voltage curve of dye sensitization solar battery, the photovoltage (Voc) that obtains opening a way is 0.76 V, and short-circuit photocurrent (Jsc) is 8.83 mA/cm
2, packing factor (FF) is 75%, effciency of energy transfer (η) is 5.1%.In addition, analyze by the intensity modulation electrochemical impedance, electric charge inhibition degree is lower than 1/10th of charge recombination degree in the battery of the similar dyestuff assembling that does not contain side group in this battery.
Embodiment 12:With dyestuff 6 is the preparation of the dye sensitization solar battery of sensitizing agent
Dyestuff 6 is dissolved in the dry toluene, be made into the solution of 0.3 mmol/L, according to the assembling of process shown in the embodiment 7 dye sensitization solar battery, under the AM1.5 simulated solar irradiation, record the current-voltage curve of dye sensitization solar battery, the photovoltage (Voc) that obtains opening a way is 0.77 V, and short-circuit photocurrent (Jsc) is 6.38 mA/cm
2, packing factor (FF) is 75%, effciency of energy transfer (η) is 3.7%.In addition, analyze by the intensity modulation electrochemical impedance, electric charge inhibition degree is lower than 1/10th of charge recombination degree in the battery of the similar dyestuff assembling that does not contain side group in this battery.
Claims (4)
1. carbazyl organic dye is characterized in that described carbazyl organic dye has following general structure:
In the formula, R
1~ R
4Be hydrogen, alkyl or aralkyl, n is 1 ~ 4 integer.
2. a kind of carbazyl organic dye according to claim 1 is characterized in that described carbazyl organic dye is any one among the structural formula 1-6:
Structural formula 1:
，
Structural formula 2:
Structural formula 3:
Structural formula 4:
Structural formula 5:
，
Structural formula 6:
3. the synthetic method of a kind of carbazyl organic dye according to claim 1 is characterized in that the synthetic route of this organic dye is as follows:
The synthetic method of this organic dye is carried out according to following steps:
(1) compound b is synthetic: under nitrogen protection, a certain amount of compound a is dissolved in the tetrahydrofuran (THF) (THF) fully, reaction system places-20 ° below the C, slowly splash into 0.9 ~ 2 times the n-Butyl Lithium that molar weight is a compound a with syringe, after low temperature reacts 0.1 ~ 2 h down, splashing into molar weight again is 1.1 ~ 2.5 times of tributyltin chlorides of compound a, after dropwising reaction system is warming up to room temperature, stir 2 ~ 36 h, reaction stops with ammonium chloride solution, uses dichloromethane extraction then, deionized water wash, use anhydrous sodium sulfate drying again, eliminate solvent and get compound b, be not further purified processing and be directly used in next step reaction;
(2) compound d is synthetic: under nitrogen protection, and with compound b, c and Pd (PPh
3)
4According to mol ratio is that the ratio of 1.1 ~ 2:1:0.005 ~ 0.2 is dissolved in N, in the dinethylformamide (DMF), more than the 80 ° of above reaction of C 4 h, eliminates solvent, and post separates to purify and obtains compound d;
(3) dyestuff e's is synthetic: with compound d, cyanoacetic acid and ammonium acetate are that the ratio of 1:1 ~ 2.5:0.05 ~ 0.5 is dissolved in the Glacial acetic acid according to mol ratio, more than refluxed under nitrogen 4 h, the methylene dichloride dilution, deionized water repeatedly washs, use anhydrous sodium sulfate drying again, eliminate solvent, post separates purification and obtains described carbazyl organic dye e.
4. use in dye sensitization solar battery according to the described a kind of carbazyl organic dye of claim 1, it is characterized in that described dye sensitization solar battery prepares through following steps:
(1) conductive glass pre-treatment: the FTO conductive glass is cut into 1.5 * 1.5 cm sizes, in acetone, ethanol and deionized water, fully clean successively, and dry up with nitrogen gas stream with ultrasonic wave;
(2) preparation of titania slurry: dropwise be added drop-wise to the different third oxygen titanium in the deionized water, and at ambient temperature more than stirring reaction 1 h, fully generate white precipitate, white precipitate is filtered, obtain titanium dioxide precipitation, this precipitation is transferred in the round bottom reaction flask, slowly drip the tetramethylammonium hydroxide aqueous solution of equivalent, add the deionized water constant volume again, powerful stirring reaction 1 ~ 5 h in 100 ~ 150 ° of C oil baths, naturally cool to room temperature, the white colloid that obtains after reaction finished is transferred in the autoclave and constant volume, hydrothermal treatment consists 6 ~ 24 h under the condition of 150 ~ 300 ° of C take out behind the naturally cooling and carry out supersound process, obtain milky TiO 2 sol;
(3) preparation of dye solution: described carbazyl organic dye is dissolved in the dry toluene, is mixed with the solution of 0.3 mmol/L;
(4) electrolytical preparation: contain 0.1 mol/L lithium iodide, 0.05 mol/L iodine, 0.6 mol/L iodo 1,2-dimethyl, the different eyeball solution of 3-n-propyl imidazoles and 0.5 mol/L 4-tert .-butylpyridine with the anhydrous acetonitrile preparation;
(5) preparation of working electrode: the resulting titania slurry of step (2) is formed one deck sol pellicle by rotation film forming, silk screen printing or pulling film forming method on clean conductive glass, dried film is put into retort furnace, temperature slowly is warming up to 450 ~ 550 ° of C, constant temperature 0.5 ~ 10 h, naturally cool to room temperature, with gained TiO
2Electrode directly immerses in the dye solution of step (3) gained and keeps 24 h;
(6) preparation of counter electrode: with the aqueous isopropanol of 0.1 ~ 50 mmol/L Platinic chloride be coated in equably clean in the step (1) and punching after conductive glass surface, place then in the retort furnace in 400 ~ 500 ° of C roasting 30 min, be cooled to room temperature and place in the moisture eliminator standby;
(7) cell package: with nitrogen gas stream with the absorption of step (5) gained the TiO of carbazyl organic dye
2The platinum counter electrode of working electrode and step (6) gained blows clean, and it is two electrodes are staggered relatively, conducting surface inwardly, thermoplastic film is inserted at the edge, heats 5 ~ 30 s under 100 ~ 120 ° of C conditions and solidifies, and the used for electrolyte syringe of step (4) the gained aperture by counter electrode is injected in the battery, and utilize wicking action to make to be full of electrolytic solution in the cavity of two electrodes, after treating the interior no bubble of two electrodes, aperture is sealed, promptly made described dye sensitization solar battery with seal gum.
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| CN103130812A (en) * | 2013-03-05 | 2013-06-05 | 华东师范大学 | Indolo[3,2,1-jk]carbazole derivative, preparation method and application |
| CN106062086A (en) * | 2014-01-16 | 2016-10-26 | 洛桑联邦理工学院 | Hole transporting and light absorbing material for solid state solar cells |
| CN104311549A (en) * | 2014-09-29 | 2015-01-28 | 浙江工业大学 | Synthetic method and application of carbazole dye sensitizer |
| CN108504131A (en) * | 2018-05-15 | 2018-09-07 | 淮阴工学院 | Carbazyl bridging D- (π-A)2Type organic dyestuff and its preparation method and application |
| CN108504131B (en) * | 2018-05-15 | 2019-07-23 | 淮阴工学院 | Carbazyl bridging D- (π-A)2Type organic dyestuff and its preparation method and application |
| CN110922392A (en) * | 2019-12-03 | 2020-03-27 | 西安近代化学研究所 | Carbazole co-sensitizer with phenyl as terminal bridge chain and preparation method thereof |
| CN110922392B (en) * | 2019-12-03 | 2023-04-18 | 西安近代化学研究所 | Carbazole co-sensitizer with phenyl as terminal bridge chain and preparation method thereof |
| CN113999217A (en) * | 2021-10-19 | 2022-02-01 | 西安近代化学研究所 | Novel compound, preparation method and application of novel compound as co-sensitizer |
| CN116199693A (en) * | 2022-12-30 | 2023-06-02 | 浙江工业大学 | Carbazole compound and preparation method and application thereof |
| CN116199693B (en) * | 2022-12-30 | 2024-09-17 | 浙江工业大学 | Carbazole compound and preparation method and application thereof |
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