CN104211691A - Carbazole-thiophene compound for dye-sensitized solar cell material and preparation method thereof - Google Patents

Carbazole-thiophene compound for dye-sensitized solar cell material and preparation method thereof Download PDF

Info

Publication number
CN104211691A
CN104211691A CN201410400119.8A CN201410400119A CN104211691A CN 104211691 A CN104211691 A CN 104211691A CN 201410400119 A CN201410400119 A CN 201410400119A CN 104211691 A CN104211691 A CN 104211691A
Authority
CN
China
Prior art keywords
carbazole
dye
compound
hexyl
solar battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410400119.8A
Other languages
Chinese (zh)
Inventor
李村
朱维菊
张晴
方敏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Anhui University
Original Assignee
Anhui University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Anhui University filed Critical Anhui University
Priority to CN201410400119.8A priority Critical patent/CN104211691A/en
Publication of CN104211691A publication Critical patent/CN104211691A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
    • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • 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
    • 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

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Hybrid Cells (AREA)

Abstract

The invention discloses a carbazole-thiophene compound for a dye-sensitized solar cell material and a preparation method thereof. The compound is a dye-sensitized solar cell material containing carbazole-thiophene groups, which is obtained by performing Knoevenagel condensation reaction on carbazole-thiophene-based aldehyde and cyanoacetic acid, and the molecular characteristic of the compound is that the structure of the compound contains N-substituted carbazole groups, thiophene groups, cyano groups and carboxyl groups; the compound has a long conjugated D-pi-A structure, simultaneously contains cyano and carboxyl, the electron-withdrawing group is cyanoacetic acid, the introduction of the thiophene group increases the length of a conjugate bridge of a dye molecule, and the compound is an ideal material as a solar cell sensitizer. The carbazole-thiophene compound has the advantages of simple synthetic route, mild reaction conditions, simple and convenient post-treatment, higher yield and convenient application.

Description

A kind of carbazole-thiophenes for dye sensitization solar battery material and preparation method thereof
Technical field
The present invention relates to a kind of for used by dye sensitization solar battery material, be specifically related to a kind of carbazole-thiophenes for dye sensitization solar battery material and preparation method thereof.
Background technology
Along with the development of social science and technology, the present situation of energy scarcity is more obvious, so the problem that people are actively seeking this environmental protection of sun power, the resourceful energy solves lack of energy.Solar cell is a kind of device sun power being changed into electric energy, and in the past few decades, solar cell obtains very fast development.Wherein the research of inorganic solar cell is the most ripe, and market degree is the highest.Inorganic solar cell mainly using the semi-conductor such as crystalline silicon and mineral compound as photochromics, the performance of its excellence in high-tech sectors such as Aeronautics and Astronautics in occupation of the status that cannot replace.But its preparation cost is high, complex process, quality are large, snappiness is poor, the shortcoming such as be difficult to prepared by big area, limits its application to a great extent.And the advantage of dye sensitization solar battery be abundant raw materials, cost is low, Technology is relatively simple; all raw material and production technique are all nontoxic, free of contamination simultaneously; portion of material can be reclaimed fully; protection human environment is had great importance, is therefore subject to the extensive concern of numerous investigators.
Organic photosensitive dyestuff is the core of dye sensitization solar battery, the spectral response of system is extended to visible region to the strong absorption of visible ray.Organic photosensitive dyestuff metal complexes has very high chemical stability, but these metals mostly are rare metal, poisonous and expensive.Pure organic dye sensitizing agent, not containing central metallic ions, has the advantages such as of a great variety, cost is lower, molar extinction coefficient is high, be convenient to carry out structure design and circulating battery is easy to operate, was developed faster in the last few years.Organic dye sensitized dose is generally made up of donor (D)-conjugated bridge (π)-acceptor (A) structure, electronics is passed to acceptor (A) by means of conjugated bridge (π) by donor (D), finally completes effective transmission of electronics.The electron donor of dyestuff, conjugated system and electron acceptor(EA) all can independently be modified, and can be changed the structure of dyestuff like this by number of ways.The electron donor of pure organic dye is generally aromatic amino-derivative, as triphenylamine, indoles, carbazole etc., generally need contain strong electron-withdrawing group group, as carboxyl etc., can ensure dye molecule and semiconductor film TiO like this in electron acceptor(EA) 2combine closely, up to the present, applying more is rhodanine-3-acetic acid or alpha-cyanoacrylate these two kinds.In addition, can also by increasing conjugated system, the absorption spectrum Einstein shift of dyestuff can be made as increased methyne number, but result also in the complexity of Dyestuff synthesis step and the reduction of dye stability while the increase of conjugated system, in order to increase conjugate system and not affect the stability of dye molecule, we can introduce the aromatic groups such as benzene, thiophene, furans, pyrroles to replace methyne.Introduce electron rich group to D system and can widen dyestuff spectral response equally.Finally, the electron-withdrawing power of acceptor A can also be increased, make dye absorber spectrum generation red shift, expand the photoresponse on long wave direction.In a word, as the dyestuff of solar cell must have uptake factor high, can the light of absorbing wavelength a wider range, energy and semi-conductor combination, there is the features such as the redox potential of comparatively mating with ionogen and good stability.
The organic dye of being used widely in dye-sensitized solar cells can be divided into coumarins dyestuff, indoline-like dyestuff, triphen amine dyestuff, tetrahydro chinolines dyestuff, dialkyl benzene amine dyestuff, fluorenes class dyestuff, perylene kinds dyestuff, porphyrin dyestuff, phthalocyanines dye, square type dye, cyanine type dye and carbazoles dyestuff etc. by structure.Carbazole is a kind of containing nitrogen compound, and be typical electron rich group, therefore carbazole derivative has good cavity transmission ability and high luminous power.Because the heterogeneous ring compounds such as nitrogenous, oxygen show good structure diversity, modify carbazole derivative with heterogeneous ring compound and prepare heterocycle carbazole derivative there is good researching value and application prospect.
Summary of the invention
The object of the invention is to provide a kind of carbazole-thiophenes for dye sensitization solar battery material and preparation method thereof for above-mentioned inorganic solar cell and organic photosensitive dyestuff metal complexes existing problems.Synthetic route of the present invention is simple, in target compound containing carboxyl, can with semi-conductor mortise, in the visible region of 400 more than nm, there is strong absorption band, the specific absorption to sunlight can be improved for sensitization solar battery.
The technical solution used in the present invention is as follows:
A kind of carbazole-thiophenes for dye sensitization solar battery material, it is characterized in that, this compound is the dye sensitization solar battery material containing carbazole-thienyl group obtained through Knoevenagel condensation reaction by aldehyde and the cyanoacetic acid based on carbazole-thiophene, and its characterization of molecules is containing N-substituted carbazole group, thienyl group, cyano group and carboxylic group in this compound structure; This compound has long conjugation D-π-A structure, cyano group and carboxyl is contained with in molecular configurational, electron-withdrawing group is cyanoacetic acid, and the introducing of thienyl group adds the conjugated bridge length of dye molecule, is as the ideal material of solar cell sensitizing agent; The chemical structural formula of described carbazole-thiophenes is as follows:
Wherein, R is carbon atom number is n=2-8 alkyl substituent.
The present invention take carbazole as raw material, N-n-hexyl carbazole is obtained through alkylation, N-n-hexyl carbazole generates 3-bromo-N-n-hexyl carbazole through NBS bromo, has synthesized dye molecule 3-(4-alpha-cyanoacrylate thiophene)-N-n-hexyl carbazole through Suzuki coupling and Knoevenagel condensation.
Synthetic route and the chemical structural formula of described carbazole-thiophenes compound are as follows:
Wherein, (1) is N-n-hexyl carbazole; (2) be 3-bromo-N-n-hexyl carbazole; (3) be 3-(4-formylthiophene)-N-n-hexyl carbazole; (4) 3-(4-alpha-cyanoacrylate thiophene)-N-n-hexyl carbazole.
The preparation method of the carbazole-thiophenes for dye sensitization solar battery material of the present invention, comprises the following steps:
(1) synthesis of N-hexyl carbazole
Carbazole is dissolved in dry DMF, stirring at room temperature adds NaH, oil sealing after dissolving completely in batches, drips the DMF solution containing bromohexane after continuing stirring at room temperature 20min by constant pressure funnel, drip and finish, 80 DEG C of water-baths reflux 3 hours stopped reaction, during cooling is fallen back, are that the salt acid for adjusting pH value of 1:1 is to neutral by volume ratio, leave standstill, separate out thick product, suction filtration, with ethyl alcohol recrystallization N-hexyl carbazole;
(2) synthesis of 3-bromo-N-n-hexyl carbazole
By N-n-hexyl carbazole, N-bromo-succinimide, benzoyl peroxide, is dissolved in dry DMF, and normal temperature lucifuge stirs 48h, cleans, has the insoluble oily liquids of deep yellow, with dichloromethane extraction, add appropriate anhydrous MgSO with large water gaging 4drying, hold over night, suction filtration is also spin-dried for organic phase, with a small amount of methylene dichloride lysate, and admixes proper silica gel, obtains faint yellow viscous liquid through column chromatography for separation;
(3) synthesis of 3-(4-formylthiophene)-N-n-hexyl carbazole
By 4-formylthiophene boric acid, 3-bromo-N-n-hexyl carbazole and saturated Na 2cO 3solution adds in there-necked flask, fills N 2protection, adds the mixing solutions of toluene and ethanol with syringe, add Pd (PPh after stirring 10min in batches 3) 4, 80 DEG C of backflow 48h.Be cooled to room temperature product is poured in large water gaging, obtain dark brown oil liquid, be extracted with ethyl acetate after stirring, saturated common salt water washing, obtain Vandyke brown liquid, add anhydrous MgSO 4drying, hold over night, suction filtration is also spin-dried for organic phase, obtains yellow 3-(4-formylthiophene)-N-n-hexyl carbazole solid with pillar layer separation;
(4) synthesis of 3-(4-alpha-cyanoacrylate thiophene)-N-n-hexyl carbazole
3-(4-formylthiophene)-N-n-hexyl carbazole is dissolved in acetonitrile and chloroform mixed solution, after all dissolving, adds cyanoacetic acid, piperidines, reflux at 80 DEG C of temperature 18h, after being cooled to room temperature, is added to the water by product, with dichloromethane extraction, the organic over anhydrous MgSO after extraction 4drying, hold over night, crude by column chromatography obtains target product.
Described in step (1), the mol ratio of carbazole and bromohexane is 5:7.
Described in step (2), the mol ratio of hexyl carbazole and NBS is 1:1.
Described in step (3), the mol ratio of toluene and ethanol is 3: 1.
The mol ratio of (4-the formylthiophene)-N-n-hexyl carbazole of 3-described in step (4) and cyanoacetic acid is 1: 3.
The dyestuff of carbazole-thiophenes that the present invention obtains is made into dye sensitization solar battery, and the electricity conversion obtained under simulated solar irradiation is 0.98%.
Beneficial effect of the present invention:
A kind of dye molecule of the present invention's synthesis has long conjugation D-π-A structure, simultaneously in molecule containing cyano group and carboxyl, electron-withdrawing group is cyanoacetic acid, containing carboxyl in this dyestuff, can with semiconductor nano TiO 2combine with the form of chemical bond, contribute to the fixing of dye in the battery, also help the transmission of electronics simultaneously; In molecule, the introducing of thienyl group adds the conjugated bridge length of dyestuff is as the ideal material of solar cell sensitizing agent; This compou nd synthesis route is simple, reaction conditions is gentle, aftertreatment is simple and convenient and productive rate is higher, is convenient to application.
Accompanying drawing explanation
Fig. 1 is the ultra-violet absorption spectrum of dyestuff 3-(4-alpha-cyanoacrylate thiophene)-N-n-hexyl carbazole in acetonitrile solution.
Fig. 2 is the fluorescence emission spectrum of dyestuff 3-(4-alpha-cyanoacrylate thiophene)-N-n-hexyl carbazole in acetonitrile.
Fig. 3 is the Cyclic voltamogram curve of dyestuff 3-(4-alpha-cyanoacrylate thiophene)-N-n-hexyl carbazole.
Fig. 4 is the photo of packaged rear dye sensitization solar battery.
Concrete case study on implementation
The present invention can be further illustrated by following embodiment, but is not only confined to embodiment.
Embodiment 1: the synthesis of dyestuff 3-(4-alpha-cyanoacrylate thiophene)-N-n-hexyl carbazole
(1) synthesis of N-hexyl carbazole
Take carbazole 1.65g (10mmol) in the round-bottomed flask that stirrer is housed, dissolve completely under adding 10mL dry DMF room temperature, then in flask, add 0.4 g NaH, oil sealing, stirred at ambient temperature 20min, dropwise adds the n-C being dissolved with 2mL by constant pressure funnel 6h 13the DMF solution 3mL of Br, 80 DEG C of oil bath backflow 3h.Be cooled to during room temperature is fallen back and fully stir, have buff white solid to generate, leave standstill to solution in clarification time suction filtration, with ethyl alcohol recrystallization, obtain white needle-like crystals, suction filtration, air-dry, obtain needle-like crystal product 1.48g, productive rate 58.85%.1H-NMR(CDCl 3,400Hz):δ(ppm):8.09(d,J＝7.6Hz,2H),7.38～7.48(m,4H),7.21(d,J＝8.0Hz,2H),4.28(t,2H),1.86(m,2H),1.33(m,6H),0.86(t,3H)。FT-IR(KBr,cm -1)：3049(＝C-H),2856-2953(-CH 2,-CH 3),1459(-CH 3),1323(-CH 2-),1621-1594(structure?of?carbazole)；
(2) synthesis of 3-bromo-N-n-hexyl carbazole
Take N-n-hexyl carbazole 2.51g (10mmol), 1.78g (10mmol) NBS, 0.05g BPO, measures 20mL dry DMF in round-bottomed flask, normal temperature lucifuge stirs 48h, clean with large water gaging, in white, and have the insoluble oily liquids of deep yellow, with dichloromethane extraction, upper strata is water, and lower floor is methylene dichloride, gets subnatant and adds appropriate anhydrous MgSO 4drying, hold over night, next day suction filtration be spin-dried for organic phase, with a small amount of methylene dichloride lysate, and admix proper silica gel, through column chromatography (eluent: petrol ether/ethyl acetate=10/1), product is dark brown viscous shape liquid 2.08g, 63.2%. 1H-NMR(400Hz,CDCl 3):δ(ppm):8.14(s,1H),7.98(d,J＝7.2Hz,1H),7.33(d,J＝8.0Hz,1H),7.47(m,2H),7.19(d，J＝8.8Hz,2H),4.17(t,2H),1.77(m,2H),1.242～1.324(m,6H),0.832(t,3H)。FT-IR(KBr,cm -1):3062(＝C-H),2951-2857(-C-H),1624-1597(structure?of?carbazole),1470(-CH 2),1350(-CH 3),802-735(Ar-H),560(-Br)；
(3) synthesis of 3-(4-formylthiophene)-N-n-hexyl carbazole
Take in 4-formylthiophene boric acid 0.94g (6mmol) there-necked flask; add stirrer, vacuumize, fill N2 protection; 1), the saturated Na of 6mL 2.5mL 3-bromo-N-n-hexyl carbazole is added, the mixing solutions of 80mL toluene and ethanol (toluene: ethanol=3: with syringe 2cO 3solution, adds Pd (PPh after stirring 10min in batches 3) 4100mg, 80 DEG C of backflow 48h.Be cooled to room temperature product to be poured in large water gaging, in dark brown oil liquid, be extracted with ethyl acetate after stirring, saturated common salt water washing, obtain Vandyke brown liquid, add anhydrous MgSO 4drying, hold over night, suction filtration be spin-dried for organic phase, with a small amount of methylene dichloride lysate, and admixed proper silica gel, through column chromatography (eluent: petrol ether/ethyl acetate=10/1), obtained yellow solid 0.31g, productive rate 31.0% next day. 1H-NMR(400Hz,CDCl 3):δ(ppm):9.88(s,1H),8.41(s,1H),8.15(s,1H),7.80(s,2H),7.46(m,4H),7.24(d,J＝8.0,1H),4.28(t,2H),1.90(m,2H),1.42(m,6H),0.90(t,3H)。FT-IR(KBr,cm -1):3047(＝C-H),2951-2853(-C-H),1699(-C＝O),1623-1593(structure?of?carbozle),1440(structure?of?thiophene),1376(-CH 3),788-725(Ar-H)；
(4) synthesis of 3-(4-alpha-cyanoacrylate thiophene)-N-n-hexyl carbazole
Taking 3-(4-formylthiophene)-N-n-hexyl carbazole 0.11g (0.3mmol) is dissolved in 10mL acetonitrile and 5mL chloroform, cyanoacetic acid 0.05g (0.82mmol) is added after all dissolving, 0.1mL piperidines, reflux at 80 DEG C of temperature 18h, after being cooled to room temperature, is added to the water by product, with dichloromethane extraction, upper strata is water, and lower floor is methylene dichloride, the organic over anhydrous MgSO after extraction 4drying, hold over night, obtains product 0.11g through column chromatography, productive rate 84.4%. 1H-NMR(400Hz,d 6-DMSO):δ(ppm):10.05(s,1H),8.50(s,1H),8.22(s,1H),7.89(s,2H),7.72(d,2H),7.63(d,2H),7.27(d,H),4.42(t,2H),1.82(m,2H),1.24(m,6H),0.90(t,3H)。FT-IR(KBr,cm -1):2926～2853(-CH 2,-CH 3),1583-1680(structure?of?carbazole),2212(-C≡N),1680(-C＝O),1412(-OH),805(structure?of?thiophene)。
The ultra-violet absorption spectrum of embodiment 2:3-(4-alpha-cyanoacrylate thiophene)-N-n-hexyl carbazole and fluorescence spectrometry
Ultraviolet-visible absorption spectroscopy measures on Shimadzu UV-3600 type ultraviolet-visible spectrophotometer, and useful range is between 200-1000nm.It is 1.0 × 10 that testing sample is made into concentration -5the test soln of mol/L.Measure its ultraviolet-visible spectrum and fluorescence spectrum respectively.Dyestuff has two absorption peaks as seen from Figure 1: be carbazole functional group π-π at the absorption peak of high energy region 291nm *charateristic avsorption band, is positioned at 426nm in the position of the absorption peak of Low Energy Region, belongs to Intramolecular electron transfer (ICT) transition of whole molecule.Analyze from uv-visible absorption spectra, the electron-withdrawing group of dyestuff is cyanoacetic acid, and the dyestuff increasing the length of conjugated bridge is ideal as solar cell sensitizing agent.
Fluorescence emission spectrum above measures at LS-55 FL spectrophotofluorometer (PerkinElmer, USA), and measurement range is 300-800nm, and sample solubility is 1.0 × 10 -5mol/L, adopt the quartz colorimetric utensil of 1cm four sides printing opacity, solvent used during test is all refined according to standard method.Fluorescence emission peak is there is as seen from Figure 2 at 565nm place.
The mensuration of the electrochemistry volt-ampere characteristic of embodiment 3:3-(4-alpha-cyanoacrylate thiophene)-N-n-hexyl carbazole
Dyestuff redox energy level is in the solution by the cyclic voltammetry of occasion China CHI660 instrument electrochemical workstation.Test have employed three electrode work systems: working electrode is glassy carbon electrode, and be Pt silk electrode to electrode, reference electrode is saturated calomel electrode.The solvent of test is trifluoroacetic acid aqueous solution.Ionogen is 0.05M tetrabutylammonium perchlorate.For reducing error, each sample all scans 3 times.
The reference electrode used in experiment is saturated calomel electrode, its current potential need be converted into standard hydrogen electrode current potential, is 0.24 eV, HOMO=eE relative to NHE current potential ox+ 0.24.Fig. 3 is the Cyclic voltamogram curve of dyestuff, and standard hydrogen electrode (NHE) current potential is-4.5 eV relative to vacuum level, so be HOMO=-(eE by the formula of electrochemical results calculating energy level ox+ 0.24+4.5 eV), LUMO=HOMO+E 0-0, cyclic voltammetric calculation result is as follows:
The HOMO of dyestuff and lumo energy be weigh its can as the important parameter of excellent sensitizing agent.Can dyestuff need meet two primary conditions as the dye sensitizing agent of DSSC: one is that the lumo energy of the dye molecule of excited state must higher than TiO 2nano crystal semiconductor conduction level (CB), so just can make the dye molecule of excited state that electronics is injected into TiO effectively 2go in nano crystal semiconductor conduction band, thus form extrinsic current; Two be ground state dye molecule HOMO energy level will lower than Oxygen in Electrolytical Solutionization reduction electricity to (I -/ I 3 -) electromotive force energy level, the dye molecule of oxidation state so just can be made to be reduced timely and then recycle.The HOMO energy level of dye molecule equals first oxidizing potential of dye molecule Cyclic voltamogram curve curve.Relation between the HOMO energy level of dye molecule and lumo energy is as follows: HOMO=LUMO+E 0-0.E 0-0being the 0-0 transition energy of dye molecule, is generally calculated by the wavelength in the ultra-violet absorption spectrum of dye molecule and fluorescence emission spectrum point of crossing.The HOMO (-0.89) of dye molecule is higher than I -/ I 3 -redox energy level (-0.5), its LUMO (1.57) is lower than TiO 2cB energy level (0.42), meet as two primary conditions of the dye sensitizing agent of dye sensitization solar battery.
Embodiment 4: the preparation of compound dye sensitization solar battery
FTO glass is coated with TiO 2-P25 film, after high temperature (400 DEG C) cures 30 minutes, immerses in the ethanolic soln of compound, takes out after 24h, and with alcohol flushing surface, then covering electrolyte solution and the FTO glass being covered with platinum film, fill with rubber seal.Prepare 4 pieces of small batteries for test simultaneously.
Embodiment 5: the test of dye sensitized nano crystal salar battery electricity conversion: to every block small battery, carry out 4 tests according to literature method, the mean value of dye sensitized nano crystal salar battery electricity conversion is: 0.98%.
Dyestuff is made into dye sensitization solar battery, the photovoltaic data obtained under simulated solar irradiation are listed in the following table, listed data carry out testing without when optimization in battery device manufacturing conditions, if wherein the electricity conversion of dyestuff is that its preparation condition is optimized by 0.98%., its electricity conversion is likely increased to about 5%-6%.
The photovoltaic data of dyestuff

Claims (7)

1. carbazole-the thiophenes for dye sensitization solar battery material, it is characterized in that, this compound is the dye sensitization solar battery material containing carbazole-thienyl group obtained through Knoevenagel condensation reaction by aldehyde and the cyanoacetic acid based on carbazole-thiophene, and its characterization of molecules is containing N-substituted carbazole group, thienyl group, cyano group and carboxylic group in this compound structure; This compound has long conjugation D-π-A structure, and simultaneously containing cyano group and carboxyl, electron-withdrawing group is cyanoacetic acid, and the introducing of thienyl group adds the conjugated bridge length of dye molecule, is as the ideal material of solar cell sensitizing agent; The chemical structural formula of described carbazole-thiophenes is as follows:
Wherein, R is carbon atom number is n=2-8 alkyl substituent.
2., as claimed in claim 1 for a preparation method for the carbazole-thiophenes of dye sensitization solar battery material, it is characterized in that comprising the following steps:
(1) synthesis of N-hexyl carbazole
Be dissolved in by carbazole in dry DMF, stirring at room temperature adds NaH, oil sealing after dissolving completely in batches, drips containing n-C after continuing stirring at room temperature 20min by constant pressure funnel 6h 13the DMF solution of Br, drips and finishes, and 80 DEG C of water-baths reflux 3 hours stopped reaction, and during cooling is fallen back, the salt acid for adjusting pH value by volume ratio being 1:1, to neutral, leave standstill, separates out thick product, suction filtration, with ethyl alcohol recrystallization N-n-hexyl carbazole;
(2) synthesis of 3-bromo-N-n-hexyl carbazole
By N-n-hexyl carbazole, N-bromo-succinimide, benzoyl peroxide, is dissolved in dry DMF, and normal temperature lucifuge stirs 48h, cleans, obtains deep yellow oily liquids, with dichloromethane extraction, add appropriate anhydrous MgSO with large water gaging 4drying, hold over night, suction filtration is also spin-dried for organic phase, with a small amount of methylene dichloride lysate, and admixes proper silica gel, obtains faint yellow viscous liquid through column chromatography for separation;
(3) synthesis of 3-(4-formylthiophene)-N-n-hexyl carbazole
By 4-formylthiophene boric acid, 3-bromo-N-n-hexyl carbazole and saturated Na 2cO 3solution adds in there-necked flask, fills N 2protection, adds the mixing solutions of toluene and ethanol with syringe, add Pd (PPh after stirring 10min in batches 3) 4, 80 DEG C of backflow 48h.Be cooled to room temperature product is poured in large water gaging, obtain dark brown oil liquid, be extracted with ethyl acetate after stirring, saturated common salt water washing, obtain Vandyke brown liquid, add anhydrous MgSO 4drying, hold over night, suction filtration is also spin-dried for organic phase, obtains yellow 3-(4-formylthiophene)-N-n-hexyl carbazole solid with pillar layer separation;
(4) synthesis of 3-(4-alpha-cyanoacrylate thiophene)-N-n-hexyl carbazole
3-(4-formylthiophene)-N-n-hexyl carbazole is dissolved in acetonitrile and chloroform mixed solution, after all dissolving, adds cyanoacetic acid, piperidines, reflux at 80 DEG C of temperature 18h, after being cooled to room temperature, is added to the water by product, with dichloromethane extraction, the organic over anhydrous MgSO after extraction 4drying, hold over night, crude by column chromatography obtains target product.
3. the preparation method of the carbazole-thiophenes for dye sensitization solar battery material according to claim 2, is characterized in that, described in step (1), the mol ratio of carbazole and bromohexane is 5:7.
4. the preparation method of the carbazole-thiophenes for dye sensitization solar battery material according to claim 2, is characterized in that, described in step (2), the mol ratio of hexyl carbazole and NBS is 1:1.
5. the preparation method of the carbazole-thiophenes for dye sensitization solar battery material according to claim 2, is characterized in that, described in step (3), the mol ratio of toluene and ethanol is 3: 1.
6. the preparation method of the carbazole-thiophenes for dye sensitization solar battery material according to claim 2, it is characterized in that, the mol ratio of (4-the formylthiophene)-N-n-hexyl carbazole of 3-described in step (4) and cyanoacetic acid is 1: 3.
7. carbazole-the thiophenes for dye sensitization solar battery material according to claim 1, it is characterized in that, the dyestuff of described compound is made into dye sensitization solar battery, and the electricity conversion obtained under simulated solar irradiation is 0.98%.
CN201410400119.8A 2014-08-13 2014-08-13 Carbazole-thiophene compound for dye-sensitized solar cell material and preparation method thereof Pending CN104211691A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410400119.8A CN104211691A (en) 2014-08-13 2014-08-13 Carbazole-thiophene compound for dye-sensitized solar cell material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410400119.8A CN104211691A (en) 2014-08-13 2014-08-13 Carbazole-thiophene compound for dye-sensitized solar cell material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN104211691A true CN104211691A (en) 2014-12-17

Family

ID=52093636

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410400119.8A Pending CN104211691A (en) 2014-08-13 2014-08-13 Carbazole-thiophene compound for dye-sensitized solar cell material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN104211691A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104628715A (en) * 2015-01-15 2015-05-20 浙江工业大学 N-phenylcarbazole compound as well as preparation method and application of compound
CN108470630A (en) * 2018-04-28 2018-08-31 东南大学 A kind of intelligence ultracapacitor combination electrode material and its preparation method and application
CN108586315A (en) * 2018-02-09 2018-09-28 浙江工业大学 A kind of benzo carbazole class compound and the preparation method and application thereof
CN109777147A (en) * 2019-01-28 2019-05-21 陕西理工大学 A kind of quick dose and preparation method thereof altogether of alkyl bithiophene -2- fluorobenzene bridging carbazole
CN110357874A (en) * 2019-08-09 2019-10-22 南京邮电大学 A kind of phenothiazinyl diazosulfide dyestuff and preparation method thereof and the dye-sensitized solar cells for using the dyestuff
CN110642830A (en) * 2019-10-21 2020-01-03 中国林业科学研究院林产化学工业研究所 Dehydroabietic acid triarylamine D-pi-A type compound with thiophene derivative as pi bridge and synthesis method thereof
CN110845489A (en) * 2019-11-13 2020-02-28 南京邮电大学 Asymmetric V-type organic dye sensitizer and preparation method and application thereof
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
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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070089784A1 (en) * 2005-10-26 2007-04-26 Noh Chang H Solar cell-driven display device and method of manufacturing thereof
US20090114283A1 (en) * 2007-11-02 2009-05-07 National Yunlin University Of Science And Technology Dye-sensitized solar cell
CN101609750A (en) * 2009-07-16 2009-12-23 长兴化学工业股份有限公司 DSSC and method for making thereof
CN101735638A (en) * 2008-11-25 2010-06-16 乐金显示有限公司 Dye for dye-sensitized solar cell and solar cell including the same
CN102453230A (en) * 2010-10-27 2012-05-16 海洋王照明科技股份有限公司 Organic semiconductor material containing carbazole and thiophene pyrrole-dione unit as well as preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070089784A1 (en) * 2005-10-26 2007-04-26 Noh Chang H Solar cell-driven display device and method of manufacturing thereof
US20090114283A1 (en) * 2007-11-02 2009-05-07 National Yunlin University Of Science And Technology Dye-sensitized solar cell
CN101735638A (en) * 2008-11-25 2010-06-16 乐金显示有限公司 Dye for dye-sensitized solar cell and solar cell including the same
CN101609750A (en) * 2009-07-16 2009-12-23 长兴化学工业股份有限公司 DSSC and method for making thereof
CN102453230A (en) * 2010-10-27 2012-05-16 海洋王照明科技股份有限公司 Organic semiconductor material containing carbazole and thiophene pyrrole-dione unit as well as preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
EUNJI LEE，等: "Synthesis of Alkyl-functionalized Organic Dyes and Their Application to Dye Sensitized Solar Cells (DSSCs)", 《BULL. KOREAN CHEM. SOC.》 *
ROMAN A IRGASHEV，等: "5-(Methylidene)barbituric acid as a new anchor unit for dye-sensitized solar cells (DSSC)", 《ARKIVOC》 *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104628715A (en) * 2015-01-15 2015-05-20 浙江工业大学 N-phenylcarbazole compound as well as preparation method and application of compound
CN108586315A (en) * 2018-02-09 2018-09-28 浙江工业大学 A kind of benzo carbazole class compound and the preparation method and application thereof
CN108470630A (en) * 2018-04-28 2018-08-31 东南大学 A kind of intelligence ultracapacitor combination electrode material and its preparation method and application
CN109777147A (en) * 2019-01-28 2019-05-21 陕西理工大学 A kind of quick dose and preparation method thereof altogether of alkyl bithiophene -2- fluorobenzene bridging carbazole
CN110357874A (en) * 2019-08-09 2019-10-22 南京邮电大学 A kind of phenothiazinyl diazosulfide dyestuff and preparation method thereof and the dye-sensitized solar cells for using the dyestuff
CN110357874B (en) * 2019-08-09 2023-01-03 南京邮电大学 Phenothiazinyl benzothiadiazole dye, preparation method thereof and dye-sensitized solar cell using same
CN110642830A (en) * 2019-10-21 2020-01-03 中国林业科学研究院林产化学工业研究所 Dehydroabietic acid triarylamine D-pi-A type compound with thiophene derivative as pi bridge and synthesis method thereof
CN110642830B (en) * 2019-10-21 2022-08-16 中国林业科学研究院林产化学工业研究所 Dehydroabietic acid triarylamine D-pi-A type compound with thiophene derivative as pi bridge and synthesis method thereof
CN110845489A (en) * 2019-11-13 2020-02-28 南京邮电大学 Asymmetric V-type organic dye sensitizer and preparation method and application thereof
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

Similar Documents

Publication Publication Date Title
CN104211691A (en) Carbazole-thiophene compound for dye-sensitized solar cell material and preparation method thereof
Zhu et al. Insight into benzothiadiazole acceptor in D–A− π–A configuration on photovoltaic performances of dye-sensitized solar cells
Alagumalai et al. Effect of out-of-plane alkyl group’s position in dye-sensitized solar cell efficiency: a structure–property relationship utilizing Indoline-based unsymmetrical squaraine dyes
Urbani et al. Meso-substituted porphyrins for dye-sensitized solar cells
Pei et al. Constructing high-efficiency D–A− π–A-featured solar cell sensitizers: a promising building block of 2, 3-diphenylquinoxaline for antiaggregation and photostability
Pei et al. Constructing Organic D–A–π‐A‐Featured Sensitizers with a Quinoxaline Unit for High‐Efficiency Solar Cells: The Effect of an Auxiliary Acceptor on the Absorption and the Energy Level Alignment
Li et al. DA-π-A featured sensitizers bearing phthalimide and benzotriazole as auxiliary acceptor: effect on absorption and charge recombination dynamics in dye-sensitized solar cells
Lu et al. Organic dyes incorporating bis-hexapropyltruxeneamino moiety for efficient dye-sensitized solar cells
Zeng et al. Efficient dye-sensitized solar cells with an organic photosensitizer featuring orderly conjugated ethylenedioxythiophene and dithienosilole blocks
He et al. New Bithiazole‐Based Sensitizers for Efficient and Stable Dye‐Sensitized Solar Cells
Zhong et al. Coumarin-bearing triarylamine sensitizers with high molar extinction coefficient for dye-sensitized solar cells
Warnan et al. A compact diketopyrrolopyrrole dye as efficient sensitizer in titanium dioxide dye-sensitized solar cells
Thongkasee et al. Carbazole-dendrimer-based donor− π–acceptor type organic dyes for dye-sensitized solar cells: effect of the size of the carbazole dendritic donor
She et al. Novel ruthenium sensitizers with a phenothiazine conjugated bipyridyl ligand for high-efficiency dye-sensitized solar cells
Shen et al. Synthesis and photovoltaic properties of powerful electron-donating indeno [1, 2-b] thiophene-based green D–A− π–A sensitizers for dye-sensitized solar cells
Bisht et al. Panchromatic sensitizer for dye-sensitized solar cells: unsymmetrical squaraine dyes incorporating benzodithiophene π-spacer with alkyl chains to extend conjugation, control the dye assembly on TiO2, and retard charge recombination
Xiang et al. The structural modification of thiophene-linked porphyrin sensitizers for dye-sensitized solar cells
Tan et al. A comparative study on properties of two phenoxazine-based dyes for dye-sensitized solar cells
Zhou et al. Multi-alkylthienyl appended porphyrins for efficient dye-sensitized solar cells
Cabau et al. Light soaking effects on charge recombination and device performance in dye sensitized solar cells based on indoline–cyclopentadithiophene chromophores
Yan et al. Efficient triarylamine–perylene dye-sensitized solar cells: influence of triple-bond insertion on charge recombination
Mao et al. Effects of donors of bodipy dyes on the performance of dye-sensitized solar cells
Bisht et al. Fused fluorenylindolenine-donor-based unsymmetrical squaraine dyes for dye-sensitized solar cells
CN105238092B (en) A kind of organic dye sensitized dose of BODIPY classes of 2,6 substitutions and preparation method thereof
Park et al. An investigation of the role the donor moiety plays in modulating the efficiency of ‘donor-π-acceptor-π-acceptor’organic DSSCs

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20141217

RJ01 Rejection of invention patent application after publication