CN105255217A - Preparation of polymer dye based on diphenylamine-azaanthracene and application to dye sensitized solar cell - Google Patents

Preparation of polymer dye based on diphenylamine-azaanthracene and application to dye sensitized solar cell Download PDF

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CN105255217A
CN105255217A CN201510726622.7A CN201510726622A CN105255217A CN 105255217 A CN105255217 A CN 105255217A CN 201510726622 A CN201510726622 A CN 201510726622A CN 105255217 A CN105255217 A CN 105255217A
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naphthazin
dye
pentanoic
anhydrous
bromo
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谭海军
姚强文
丘志安
肖玉赐
陈宗满
蔡大莹
冉艾灵
黎小凤
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Guilin University of Technology
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Guilin University of Technology
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    • Y02E10/542—Dye sensitized solar cells

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Abstract

The invention discloses preparation of a polymer dye based on diphenylamine-azaanthracene and application to a dye sensitized solar cell. Diphenylamine, azaanthracene, fluorene and the like form an electron supplying conjugated main chain structure and a side chain is connected with the azaanthracene, thiophene and a derivative bridging unit thereof; cyanoacetic acid is used as an electron absorption unit, and the cyanoacetic acid, carbazole, the fluorene, and the azaanthracene form the polymer dye based on the diphenylamine-azaanthracene; the polymer dye is applied to the dye sensitized solar cell. The polymer dye provided by the invention has a simple synthesis process and low cost, and is easy to separate and purify; a polymer molecular design is easy to cut; the mol light absorption coefficient and the heat stability of the polymer dye are better than those of a micro-molecular dye; the polymer dye provided by the invention is applied to the dye sensitized solar cell ad the photoelectrical power conversion efficiency is 5.6%; furthermore, the invention proves a research application prospect of the polymer in the field of the dye sensitized solar cell.

Description

Based on the preparation of the polymeric dye of pentanoic-naphthazin(e) and the application in dye sensitization solar battery
Technical field
The invention belongs to polymeric dye sensitization solar battery field, particularly the design and synthesis of polymeric dye and the application in dye sensitization solar battery thereof.
Background technology
Dye sensitization solar battery (DSC) studies the novel solar battery that a more class most possibly replaces conventional inorganic silicon solar cell this year.Dyestuff, as the important component part of DSC, plays decisive role to its performance.Dyestuff based on metal complexes shows good performance (CN200910067079.9) in DSC, that current DSC field is most effective is zinc protoporphyrin metal complexes (YD2-o-C8), its efficiency is 12.3% (AswaniYella, Michael etal.Science, 2011,334:629-633).But due to resource limit and the environmental problem of precious metal, make nonmetal pure organic dyestuff become the focus of dyestuff exploitation in DSC in recent years.It is simple that pure organic dye has Molecular Structure Design synthesis for precious metals complex dyestuff, raw material sources are extensive, and molar extinction coefficient is advantages of higher (CN200910010809.1, CN201210048639.8 comparatively, CN201210048639.8, CN201210178977.3).
In recent years, conducting polymer composite is applied to the field such as Organic Light Emitting Diode, polymer solar battery and has large quantity research report.For this reason, some investigators wish the advantage utilizing conducting polymer composite, and exploitation has the dye-sensitized cell of more high conversion efficiency and stability.Because, compared to small molecule dyes, polymeric dye has many potential advantages: can use for reference a large amount of classical architecture unit from small molecule dyes and polymer solar battery (PSC) material on the one hand, and the leeway that its Molecular Structure Design is selected is larger than small molecules.On the other hand, utilize the better thermotolerance of polymer, solvent resistance and film-forming properties, dyestuff can be improved at TiO 2absorption stability on film.Utilize the blocking effect of polymeric membrane in addition, likely suppress better to inject TiO 2electronics and electrolytic solution in reduce ion I 3 -compound.2011, KirkS.Schanze etc. have synthesized a kind of 4,7-bis-(3-carboxy thiophene)-2,1,3-diazosulfide and 3,4-dioctyl thiophene copolymers dyestuff, DSSC device efficiency 2.99% (ZhenFang, AaronA.Eshbaugh, KirkS.Schanze.J.Am.Chem.Soc.2011,133,3063 – 3069).2009, Binliu etc. have synthesized containing the middle D-π-A type polymeric dye P2 be connected with conjugation thiophene unit (π) of an electron donor(ED) (D) and an electron acceptor(EA) (A) (alpha-cyanoacrylate) first, DSSC device efficiency of conversion is 3.39% (WeiZhang, ZhenFang, BinLiu, et.al.Macromol.RapidCommun.2009,30,1533-1537).2011, it was that alpha-cyanoacrylate is acceptor, and bithiophene is the D-π-A type polymeric dye RCP-1 of conjugated pi unit, and efficiency reaches 4.11% to body that Jongbeombeak etc. have synthesized with carbazole-thiophene copolymers.(DongWookChang,LimingDai,Jong-BeomBaek.et.al.Macromol.RapidCommun.2011,32,1809-1814)。Within 2013, applicant has synthesized a series of polymer dye molecules based on triphenylamine, carbazole, thiodiphenylamine unit, and on main chain, introduce long alkyl chain to strengthen the flexibility of molecule, in addition, connecting thiophene and derivatives at side chain is bridging unit and the electrophilic unit of cyanoacetic acid, and most high-photoelectric transformation efficiency reaches 4.4%.(HaijunTan,ChunyuePan,GangWang.Et.al.RSCAdv.,2013,3,16612-16618)。
Based on above research experience, the present invention, in conjunction with pentanoic, naphthazin(e) unit, has prepared a series of polymer dye molecules, and have studied its application performance in DSC.
Summary of the invention
The object of this invention is to provide a kind of preparation method of organic polymer dyestuff and the application in dye sensitization solar battery, this kind of dyestuff is to electron conjugated backbone structure with pentanoic, naphthazin(e), fluorenes etc., side chain connects naphthazin(e), thiophene and derivatives bridging unit, take cyanoacetic acid as electrophilic unit, this kind of dyestuff has good application performance in DSC.
The polymeric dye based on pentanoic-naphthazin(e) that the present invention relates to has following chemical structure of general formula 1:
In general formula 1, D 2for:
In general formula 1, π is:
In general formula 1, X is: O, S.
In general formula 1, R is:
Preparation method's concrete steps based on the polymeric dye of pentanoic-naphthazin(e) are:
Getting R in general formula 1 is iso-octyl, and π unit is thiophene, and A is alpha-cyanoacrylate; When π unit is different from R unit, the synthetic method of dyestuff is identical with following method.
(1) in there-necked flask, 2-4gN-iso-octyl naphthazin(e) is dissolved in 10-30mL anhydrous tetrahydro furan (THF) solution; Then the anhydrous tetrahydrofuran solution of 10-30mL containing 1-3gN-bromo-succinimide (NBS) is slowly dripped with constant pressure funnel, within 1 hour, drip off, ice-water bath reaction 8-12 hour, be spin-dried for solvent, crude product column chromatography separating purification, sherwood oil makees eluent, obtained 2-bromo naphthazin(e).
(2) 2.5-5g step (1) gained 2-bromo naphthazin(e) and 1-2g5-formylthiophene-2-boric acid are dissolved in 40-60mL anhydrous tetrahydro furan (THF) solution, then add 2-3g anhydrous potassium sulfate and 0.05-0.15gPd (PPh 3) 4, under nitrogen protection condition, 60-80 DEG C is refluxed 24 hours; Cooling, removing organic solvent, methylene dichloride dissolves, distillation washing three times, and merge organic phase, anhydrous sodium sulfate drying, filtration is spin-dried for, crude product column chromatography separating purification, obtained 2-thiophene aldehyde-naphthazin(e).
(3) 1g step (2) gained 2-thiophene aldehyde-naphthazin(e) is dissolved in 10-30mL anhydrous tetrahydro furan (THF) solution, then anhydrous tetrahydro furan (THF) solution of 10-30mL containing 0.1-1gN-bromo-succinimide (NBS) is slowly dripped, within 1 hour, drip off, ice-water bath reaction is to complete, be spin-dried for solvent, dichloromethane solution dissolves, distillation washing 3 times, organic over anhydrous dried over mgso, filter, be spin-dried for, crude product column chromatography separating purification, the obtained bromo-2-of 7-(4-formylthiophene)-naphthazin(e).
(4) the bromo-2-of 1.5-4g step (3) gained 7-(4-formylthiophene)-naphthazin(e) and 1.0g pentanoic are dissolved in 20-40mL anhydrous toluene solution, then add 0.01-0.1gPd (OAc) 2, 0.1-1gt-BuOK and 0.1-1mL analytical pure P (t-Bu) 3, argon shield, reaction is spent the night, cooling; then be extracted with ethyl acetate, organic layer saturated common salt washes 3 times, organic over anhydrous dried over mgso, filters; be spin-dried for, crude product column chromatography separating purification, obtained 7-pentanoic-2-(4-formylthiophene)-naphthazin(e).
(5) 1.5-4g step (4) gained 7-pentanoic-2-(4-formylthiophene)-naphthazin(e) is dissolved in 90-110mL anhydrous tetrahydro furan (THF), 1-2gN-bromo-succinimide (NBS) is dripped under lucifuge, 0 DEG C of condition, within 1 hour, drip off, 0 DEG C is reacted 1 hour, move to room temperature reaction 12 hours, distilled water quencher is reacted, be spin-dried for solvent, anhydrous methylene chloride extracts, organic over anhydrous dried over mgso, is spin-dried for, purification by column chromatography, obtained monomer 7-(4,4 '-two bromo-pentanoic)-2-(4-formylthiophene)-naphthazin(e).
(6) by 0.5-1.5g step (5) gained 7-(4,4 '-two bromo-pentanoic)-3-(4-formylthiophene)-thiodiphenylamine, 0.1-1g thiodiphenylamine diborate and 0.05-0.2gPd (pph 3) 4join in 10mL dry toluene, then add the K that 3mL concentration is 2mol/L 2cO 3; 100 DEG C of polymer reactions 48 hours; Pour in 250mL absolute methanol solution, collected by filtration, precipitation anhydrous methanol, normal hexane respectively rope carry 24 hours, finally use CHCl 3extract 24 hours, obtain black solid namely.
(7) 0.5-1.5g step (6) products therefrom, 0.1-0.4g cyanoacetic acid and 10-30mL analytical pure chloroform are added reaction flask; Nitrogen protection, stirring and dissolving; Use syringe to squeeze into 0.6-1mL analytical pure piperidines, temperature rising reflux, react 7 hours; Being cooled to room temperature after reacting completely, is hydrochloric acid soln and the saturated common salt water washing of 2mol/L successively by concentration; Organic phase merges, anhydrous magnesium sulfate drying; Filter, revolve and steam except desolventizing, obtain dark red solid namely based on the polymeric dye of pentanoic-naphthazin(e).
Preparation based on the dye sensitization solar battery of the polymeric dye of pentanoic-naphthazin(e):
(1) based on the polymeric dye sensitization solar battery of pentanoic-naphthazin(e) by transparent substrates, light trapping layer, ionogen, form electrode.Transparent substrates and to dividing lighting trapping layer and ionogen successively in the middle of electrode, wherein, described transparent base layer is conductive glass (FTO/ITO); Described smooth trapping layer is by semiconductor nano titanium dioxide layer (TiO 2, median size is between 0-50nm) and dye coating form; Described dielectric substrate is iodine/lithium iodide ionogen; Described is the conductive glass plating Pt to electrode; Described dye coating is the polymeric dye based on pentanoic-naphthazin(e) described in general structure 1.
(2) transparent substrates of dye sensitization solar battery is FTO or ITO bought, the nano-TiO then adopting the method for silk screen printing to coat two-layer particle diameter on a transparent substrate to differ 2film, underlayer thickness is 7 μm, and particle diameter is 20nm, and upper strata particle diameter is 400nm, and thickness is 5 μm.About the concrete preparation method of light trapping layer is see document: (TanHaijun.Et.al., SynthsisandCharacterizationofConjugatedpolymerswithMain-chainDonorsandPendentp-AcceptorforDye-SensitizedSolarCel ls.RSCAdv., 2013,3,16612 – 16618).
By the above-mentioned light anode prepared 500 DEG C of thermal treatments 30 minutes, after naturally cooling to 80 DEG C, put into polymer dye solution (5 × 10 -4mol/L tetrahydrofuran (THF)) in, sensitization 12 hours; Clean with acetonitrile after sensitization and dry up stand-by.
(3) on pretreated FTO conducting glass substrate, plating Pt does electrode; Light anode good for sensitization is upwards positioned on thermocompressor, at TiO 2the Surlyn ring that around film, 30 μm, cover is thick, covers electrode, then 100 DEG C of heat-sealings 2 minutes; Dripping 1 ionogen on the aperture of electrode, after using surge pump to vacuumize there is no bubble between two electrodes that make, seal, obtain dye sensitization solar battery.
Polymeric dye building-up process provided by the invention is simple, and with low cost, be easy to separating-purifying, Polymer supported catalyst is cut out easily; The molar absorptivity of polymeric dye and thermostability comparatively small molecule dyes are good; This kind of polymeric dye is applied in dye sensitization solar battery and obtains photoelectric power efficiency of conversion 5.6% by the present invention, demonstrates the research application prospect of polymkeric substance in field of dye-sensitized solar cells further.
Accompanying drawing explanation
Fig. 1 is the synthetic route of pentanoic of the present invention-naphthazin(e) class monomer.
Fig. 2 is the synthetic route of the polymeric dye that the present invention is based on pentanoic-naphthazin(e).
Fig. 3 is the ultraviolet-visible spectrogram of the embodiment of the present invention based on the polymeric dye (PDPAPTZ) of pentanoic-naphthazin(e).
Fig. 4 is the photoelectric current-voltage spectroscopy (I-V curve) of the embodiment of the present invention based on the polymeric dye (PDPAPTZ) of pentanoic-naphthazin(e).
Fig. 5 is the structural representation of the embodiment of the present invention based on polymeric dye (PDPAPTZ) sensitization solar battery of pentanoic-naphthazin(e).
Mark in figure: 1-transparent substrates; 2-light trapping layer; 3-ionogen; 4-is to electrode; 5-semiconductor nano titanium dioxide layer; 6-dye coating; 7-Surlyn ring.
Embodiment
Embodiment:
When in the polymeric dye based on pentanoic-naphthazin(e) (PDPAPTZ) described in general formula 1, naphthazin(e) is thiodiphenylamine, D 2also be thiodiphenylamine, π unit is thiophene, and when A is alpha-cyanoacrylate, the structure based on the polymeric dye (PDPAPTZ) of pentanoic-naphthazin(e) is as follows:
One, based on the synthesis of the polymeric dye (PDPAPTZ) of pentanoic-naphthazin(e)
(1) synthesis of the bromo-thiodiphenylamine of 3-
2.95gN-iso-octyl thiodiphenylamine piperazine is dissolved in 20mL anhydrous tetrahydro furan (THF); Stirring and dissolving, then 20mL is slowly added drop-wise to containing in anhydrous tetrahydro furan (THF) solution of 1.78gN-bromo-succinimide (NBS), within 1 hour, drip off, ice-water bath reaction is to complete, be spin-dried for solvent, crude product, with column chromatography separating purification (sherwood oil), obtains pale yellow oil and the bromo-thiodiphenylamine of 3-, productive rate: 3.24g, 86.6%.Hydrogen spectrum is 1hNMR (CDCl3,400MHz), (TMS, ppm): 6.87-6.84 (m, 1H), 6.80-6.76 (t, 1H), 6.74-6.73 (m, 1H), 6.62-6.59 (d, 2H), 6.52-6.50 (d, 1H), 6.35-6.33 (d, 1H), 1.83-1.81 (m, 1H), 1.45-1.25 (m, 10H), 0.92-0.86 (m, 6H) .GC-MS:m/z=373.1.
(2) synthesis of 3-(4-formylthiophene)-thiodiphenylamine
3.24g3-bromo thiodiphenylamine and 1.5g5-formylthiophene-2-boric acid are dissolved in 50mL anhydrous tetrahydro furan (THF), then add 2.6g anhydrous potassium sulfate and 0.10gPd (PPh 3) 4, under nitrogen protection condition, 70 DEG C are refluxed 24 hours.Cooling, be spin-dried for, methylene dichloride dissolves, wash 3 times, merge organic phase, anhydrous sodium sulfate drying, filtration is spin-dried for, crude product pillar layer separation (analytical pure methylene dichloride: the volume ratio of analytical pure sherwood oil is 1:4) obtains orange solids and 3-(4-formylthiophene)-thiodiphenylamine, productive rate: 1.2g (33.8%).Hydrogen spectrum is 1hNMR (CDCl 3, 400MHz), (TMS, ppm): 9.84 (s, 1H), 7.69-7.68 (m, 1H), 7.23-7.21 (m, 1H), 7.13-7.10 (m, 1H), 6.91-6.88 (m, 1H), 6.80-6.77 (m, 1H), 6.65 (m, 1H), 6.53-6.51 (d, 1H), 6.40-6.38 (d, 1H), 1.91-1.88 (m, 1H), 1.55-1.29 (m, 10H), 0.95-0.87 (m, 6H) .GC-MS:m/z=405.5
(3) synthesis of the bromo-3-of 7-(4-formylthiophene)-thiodiphenylamine
1g3-(4-formylthiophene)-thiodiphenylamine is dissolved in 20mL anhydrous THF solution, then the anhydrous THF solution of 20mL containing 0.44gN-bromo-succinimide (NBS) is slowly dripped, within 1 hour, drip off, ice-water bath reaction is to complete, be spin-dried for solvent, dichloromethane solution dissolves, wash 3 times, organic over anhydrous dried over mgso, filter, be spin-dried for, crude product column chromatography separating purification (analytical pure methylene dichloride: analytical pure sherwood oil volume ratio is 1:4) obtains yellow solid and the bromo-3-of 7-(4-formylthiophene)-thiodiphenylamine, productive rate: 0.582g, 48.9%.Hydrogen spectrum is 1hNMR (CDCl 3, 400MHz), (TMS, ppm): 9.86 (s, 1H), 7.71-7.70 (d, 1H), 7.47-7.42 (m, 2H), 7.29-7.26 (m, 3H), 6.89-6.87 (d, 1H), 6.75-6.72 (d, 1H), 1.91-1.88 (m, 1H), 1.45-1.33 (m, 4H), 1.28-1.25 (m, 6H), 0.88-0.85 (m, 6H) .GC-MS:m/z=485.1
(4) synthesis of 7-pentanoic-3-(4-formylthiophene)-thiodiphenylamine
The bromo-3-of 2.36g step (3) gained 7-(4-formylthiophene)-thiodiphenylamine and 1.0g pentanoic are dissolved in 30mL toluene solution, then add 0.050gPd (OAc) 2, 0.41gt-BuOK and 0.4mL analytical pure P (t-Bu) 3argon shield; reaction is spent the night, and cooling, is then extracted with ethyl acetate; the saturated NaCl solution of organic layer washes 3 times; organic over anhydrous dried over mgso, filters, is spin-dried for; crude product column chromatography separating purification (analytical pure sherwood oil: analytical pure ethyl acetate volume ratio is 10:1) obtains orange/yellow solid and 7-pentanoic-3-(4-formylthiophene)-thiodiphenylamine, productive rate: 1.45g (52%).Hydrogen spectrum is 1hNMR (CDCl 3, 400MHz), (TMS, ppm): δ=9.61 (s, 1H), 7.6-7.55 (d, 1H), 7.13-7.06 (d, 1H), 7.01-6.93 (m, 4H), 6.88-6.82 (m, 2H), 6.62-6.55 (m, 2H), 6.46-6.45 (m, 4H), 6.14 (s, 1H), 5.96-5.88 (d, 2H), 2.61 (m, 1H), 0.96-1.52 (m, 14H) .GC-MS:m/z=558.1.
(5) synthesis of 7-(4,4 '-two bromo-pentanoic)-3-(4-formylthiophene)-thiodiphenylamine
2.23g step (4) gained 7-pentanoic-3-(4-formylthiophene)-thiodiphenylamine is dissolved in 100mL anhydrous tetrahydro furan (THF), anhydrous tetrahydro furan (THF) solution of 20mL containing 1.4gN-bromo-succinimide (NBS) is dripped under lucifuge, 0 DEG C of condition, within 1 hour, drip off, react 1 hour, move to room temperature reaction 12 hours, water quencher is reacted, and is spin-dried for solvent, with 100mL analytical pure CH 2cl 2dissolve, which floor has use anhydrous MgSO 4drying, is spin-dried for, purification by column chromatography (PE/CH 2cl 2=4/1-2/1, v/v) obtain yellow powder and 7-(4,4 '-two bromo-pentanoic)-3-(4-formylthiophene)-thiodiphenylamine, productive rate: 1.93g, 89.4%.Hydrogen spectrum is 1hNMR (CDCl 3, 400MHz, ppm): δ=9.88 (s, 1H), 7.88-7.75 (d, 1H), 7.33-7.26 (d, 1H), 7.18-7.13 (m, 4H), 6.98-6.88 (m, 2H), 6.66-6.55 (m, 4H), 6.24 (s, 1H), 6.02-5.93 (d, 2H), 2.61 (m, 1H), 0.96-1.52 (m, 14H) .GC-MS:m/z=716.3.
(6) by 0.716g step (5) gained 7-(4,4 '-two bromo-pentanoic)-3-(4-formylthiophene)-thiodiphenylamine, 0.549g thiodiphenylamine diborate and 0.1gPd (pph 3) 4join in 10mL dry toluene, add the K that 3mL concentration is 2mol/L 2cO 3; 100 DEG C of polymer reactions 48 hours; Pour in 250mL absolute methanol solution, collected by filtration, precipitation anhydrous methanol, normal hexane respectively rope carry 24 hours, finally use CHCl 3extract 24 hours, obtain black solid, productive rate: 0.75g, 88.1%.Hydrogen spectrum is 1hNMR (CDCl 3, 400MHz, ppm): 9.88 (s, 1H), 8.10 (m, 2H), 7.90 (s, 1H), 7.87 (s, 5H), 7.70 (s, 1H), 7.58 (m, 5H), 7.45 (s, 4H), 7.23 (d, 2H), 2.43-1.33 (m, 24H), 0.80 (m, 6H).
(7) 0.75g step (6) products therefrom, 0.212g cyanoacetic acid and 20mL analytical pure chloroform are added reaction flask; Nitrogen protection, stirring and dissolving; Use syringe to squeeze into 0.8mL analytical pure piperidines, temperature rising reflux, react 7 hours; Being cooled to room temperature after reacting completely, is hydrochloric acid soln and the saturated common salt water washing of 2mol/L successively by concentration; Organic phase merges, anhydrous magnesium sulfate drying; Filter, revolve and steam except desolventizing, obtain dark red solid namely based on the polymeric dye of pentanoic-naphthazin(e), productive rate: 0.51g, 55.4%.Hydrogen spectrum is 1hNMR (DMSO, 400MHz, ppm): 8.51 (s, 1H), 8.3-7.1 (m, 19H) .GPC:(THF, polystyrenestandard), Mn=2.263kgmol -1, Mw=2.921kgmol -1, PDI=1.37.
Two, based on the fabrication & properties of the dye sensitization solar battery of the polymeric dye (PDPAPTZ) of pentanoic-naphthazin(e):
(1) as shown in Figure 3, based on polymeric dye (PDPAPTZ) sensitization solar battery of pentanoic-naphthazin(e) by transparent substrates 1, light trapping layer 2, ionogen 3, form electrode 4.Transparent substrates 1 and to dividing lighting trapping layer 2 and ionogen 3 successively in the middle of electrode 4, wherein, described transparent base layer 1 is conductive glass (FTO/ITO); Described smooth trapping layer 2 is by semiconductor nano titanium dioxide layer 5 (TiO 2, median size is between 0-50nm) and dye coating 6 form; Described dielectric substrate 3 is iodine/lithium iodide ionogen; Described is the conductive glass plating Pt to electrode 4; Described dye coating 6 is the polymeric dye (PDPAPTZ) based on pentanoic-naphthazin(e) described in general structure 1.
(2) transparent substrates of dye sensitization solar battery is FTO or ITO bought, the nano-TiO then adopting the method for silk screen printing to coat two-layer particle diameter on a transparent substrate to differ 2film, underlayer thickness is 7 μm, and particle diameter is 20nm, and upper strata particle diameter is 400nm, and thickness is 5 μm.About the concrete preparation method of light trapping layer is see document: (TanHaijun.Et.al., SynthsisandCharacterizationofConjugatedpolymerswithMain-chainDonorsandPendentp-AcceptorforDye-SensitizedSolarCel ls.RSCAdv., 2013,3,16612 – 16618).
By the above-mentioned light anode prepared 500 DEG C of thermal treatments 30 minutes, after naturally cooling to 80 DEG C, put into polymer dye solution (5 × 10 -4mol/L tetrahydrofuran (THF)) in, sensitization 12 hours; Clean with acetonitrile after sensitization and dry up stand-by.
(3) on pretreated FTO conducting glass substrate, plating Pt does electrode 4; Light anode good for sensitization is upwards positioned on thermocompressor, at TiO 2the Surlyn ring 7 that around film, 30 μm, cover is thick, covers electrode 4, then 100 DEG C of heat-sealings 2 minutes; Aperture to electrode 4 drips 1 ionogen 3, after using surge pump to vacuumize there is no bubble between two electrodes that make, seal, obtain dye sensitization solar battery.
Device measures under standard A M1.5 simulated solar irradiation, light intensity 100mw/cm -2, the short-circuit current J recorded scfor 9.72mA/cm -2, open circuit voltage V ocfor 781mV, packing factor ff is 0.73, photoelectric transformation efficiency η is 5.6%.

Claims (3)

1., based on a polymeric dye for pentanoic-naphthazin(e), it is characterized in that there is following chemical structure of general formula 1:
In general formula 1, D 2for:
In general formula 1, π is:
In general formula 1, X is: O or S;
In general formula 1, R is:
flexible group.
2. the preparation method of the polymeric dye based on pentanoic-naphthazin(e) according to claim 1, is characterized in that concrete steps are:
Getting R in general formula 1 is iso-octyl, and π unit is thiophene, and A is alpha-cyanoacrylate; When π unit is different from R unit, synthetic method is also identical;
(1) in there-necked flask, 2-4gN-iso-octyl naphthazin(e) is dissolved in 10-30mL anhydrous tetrahydrofuran solution; Then slowly drip the anhydrous tetrahydrofuran solution of 10-30mL containing 1-3gN-bromo-succinimide with constant pressure funnel, within 1 hour, drip off, ice-water bath reaction 8-12 hour, be spin-dried for solvent, crude product column chromatography separating purification, sherwood oil makees eluent, obtained 2-bromo naphthazin(e);
(2) 2.5-5g step (1) gained 2-bromo naphthazin(e) and 1-2g5-formylthiophene-2-boric acid are dissolved in 40-60mL anhydrous tetrahydro furan (THF) solution, then add 2-3g anhydrous potassium sulfate and 0.05-0.15gPd (PPh 3) 4, under nitrogen protection condition, 60-80 DEG C is refluxed 24 hours; Cooling, removing organic solvent, methylene dichloride dissolves, distillation washing three times, and merge organic phase, anhydrous sodium sulfate drying, filtration is spin-dried for, crude product column chromatography separating purification, obtained 2-thiophene aldehyde-naphthazin(e);
(3) 1g step (2) gained 2-thiophene aldehyde-naphthazin(e) is dissolved in 10-30mL anhydrous tetrahydrofuran solution, then the anhydrous tetrahydrofuran solution of 10-30mL containing 0.1-1gN-bromo-succinimide (NBS) is slowly dripped, within 1 hour, drip off, ice-water bath reaction is to complete, be spin-dried for solvent, dichloromethane solution dissolves, distillation washing 3 times, organic over anhydrous dried over mgso, filter, be spin-dried for, crude product column chromatography separating purification, the obtained bromo-2-of 7-(4-formylthiophene)-naphthazin(e);
(4) the bromo-2-of 1.5-4g step (3) gained 7-(4-formylthiophene)-naphthazin(e) and 1.0g pentanoic are dissolved in 20-40mL anhydrous toluene solution, then add 0.01-0.1gPd (OAc) 2, 0.1-1gt-BuOK and 0.1-1mLP (t-Bu) 3, argon shield, reaction is spent the night, cooling, then be extracted with ethyl acetate, organic layer saturated common salt washes 3 times, organic over anhydrous dried over mgso, filters, be spin-dried for, crude product column chromatography separating purification, obtained 7-pentanoic-2-(4-formylthiophene)-naphthazin(e);
(5) 1.5-4g step (4) gained 7-pentanoic-2-(4-formylthiophene)-naphthazin(e) is dissolved in 90-110mL anhydrous tetrahydro furan, 1-2gN-bromo-succinimide is dripped under lucifuge, 0 DEG C of condition, within 1 hour, drip off, 0 DEG C is reacted 1 hour, move to room temperature reaction 12 hours, distilled water quencher is reacted, be spin-dried for solvent, anhydrous methylene chloride extracts, organic over anhydrous dried over mgso, is spin-dried for, purification by column chromatography, obtained monomer 7-(4,4 '-two bromo-pentanoic)-2-(4-formylthiophene)-naphthazin(e);
(6) by 0.5-1.5g step (5) gained 7-(4,4 '-two bromo-pentanoic)-3-(4-formylthiophene)-thiodiphenylamine, 0.1-1g thiodiphenylamine diborate and 0.05-0.2gPd (pph 3) 4join in 10mL dry toluene, then add the K that 3mL concentration is 2mol/L 2cO 3; 100 DEG C of polymer reactions 48 hours; Pour in 250mL absolute methanol solution, collected by filtration, precipitation anhydrous methanol, normal hexane respectively rope carry 24 hours, finally use CHCl 3extract 24 hours, obtain black solid namely;
(7) 0.5-1.5g step (6) products therefrom, 0.1-0.4g cyanoacetic acid and 10-30mL analytical pure chloroform are added reaction flask; Nitrogen protection, stirring and dissolving; Use syringe to squeeze into 0.6-1mL analytical pure piperidines, temperature rising reflux, react 7 hours; Being cooled to room temperature after reacting completely, is hydrochloric acid soln and the saturated common salt water washing of 2mol/L successively by concentration; Organic phase merges, anhydrous magnesium sulfate drying; Filter, revolve and steam except desolventizing, obtain dark red solid namely based on the polymeric dye of pentanoic-naphthazin(e).
3. the application of the polymeric dye based on pentanoic-naphthazin(e) according to claim 1 and 2, is characterized in that the polymeric dye based on pentanoic-naphthazin(e) is applied in dye sensitization solar battery.
CN201510726622.7A 2015-10-29 2015-10-29 Preparation of polymer dye based on diphenylamine-azaanthracene and application to dye sensitized solar cell Pending CN105255217A (en)

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