CN101514262A - Ethylene naphthalene and paradiazine dye and application thereof to dye-sensitized solar cells. - Google Patents
Ethylene naphthalene and paradiazine dye and application thereof to dye-sensitized solar cells. Download PDFInfo
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- CN101514262A CN101514262A CN 200910010809 CN200910010809A CN101514262A CN 101514262 A CN101514262 A CN 101514262A CN 200910010809 CN200910010809 CN 200910010809 CN 200910010809 A CN200910010809 A CN 200910010809A CN 101514262 A CN101514262 A CN 101514262A
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- 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
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- 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
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Abstract
The invention relates to the application field of photoelectric conversion materials in the fine chemistry industry, in particular to ethylene naphthalene and paradiazine dye and application thereof to dye-sensitized solar cells. The dye is characterized by taking ethylene naphthalene and paradiazine and derivatives thereof as a conjugated system, one end of the conjugated system is connected with adjacent dicarboxyl or a single carboxyl as electron withdraw group which is used to be absorbed on TiO2, and the other end thereof is connected with different electron-donating groups to form an electric push-pull type organic dye. As taking the ethylene naphthalene and paradiazine as the conjugated system ensures a fine plane structure, by connecting the conjugated system with the electron group and the electron-withdrawing group, electrons are easy to transfer in case of excited state and the dye is led to generate unique photoelectrochemical property, therefore enjoying fine application performance in dye-sensitized solar cells; in addition, the ethylene naphthalene and paradiazine dye features simple synthetic method and easily available raw materials, thus being capable of replacing noble metal photosensitive dyes with relatively high price and effectively reducing the cost of the dye-sensitized solar cells.
Description
Technical field
The invention belongs to the photoelectricity converting material Application Areas in the fine chemistry industry, be specifically related to a class with acenaphthene and pyrazine and derivative thereof as conjugated system, an end connects adjacent dicarboxyl or single carboxyl is an electron-withdrawing group, is used for being adsorbed on TiO
2On, the other end connects different electron-donating groups, and form an electron-like and push away-pull-up dyestuff, and the application of described dyestuff in dye sensitization solar battery.
Background technology
Dye sensitization solar battery is the M. of Switzerland in 1991
A kind of new type solar energy that professor proposes is converted into the device of electric energy, its composition is generally: adsorbed the nanoporous sull of light-sensitive coloring agent and the light anode that transparent conductive substrate is formed, the conductive glass of plating Pt is a photocathode, is filled in ionogen and sealing material between two electrodes.This class battery has advantages such as simple in structure, that cost of manufacture is low, and its electricity conversion can reach more than 10% at present, is the photoelectric conversion device that a class has application prospect.Light-sensitive coloring agent is a very important part in the dye sensitization solar battery, and the structure design of dyestuff is most important for this class battery.Use at present maximum M. that is
The N3 and the N719 dyestuff of the invention of professor seminar, these two dyestuffs are the ruthenium complexe dyestuff, make that the cost of this class dyestuff is higher relatively owing to introduced precious metal, thereby have limited its application.Organic photosensitive dyestuff development numerous in variety in recent years is rapid, and in order further to reduce the dye sensitization solar battery cost, the present invention designs and synthesized novel acenaphthene and the pyrazine class organic photosensitive dyestuff of a class.
Summary of the invention
The purpose of this invention is to provide the novel organic photosensitive dyestuff of a class, this class dyestuff is to be conjugated system with the acenaphthene that replaces and pyrazine and derivative thereof, and an end connects adjacent dicarboxyl or single carboxyl is an electron-withdrawing group, is used for being adsorbed on TiO
2On, the other end connects different electron-donating groups, forms an electron-like and pushes away-pull-up compound.This class dyestuff has good application performance on dye sensitization solar battery.
The concrete technical scheme of the present invention, that is:
One class is used for the acenaphthene and the pyrazine dyestuff of dye sensitization solar battery, has following general structure:
Wherein, m is 0～1 integer; Among A, the B one when being carboxyl, another is hydrogen or carboxyl;
In the formula: X
1Be C
1～C
4Straight chained alkyl.
The synthetic method of acenaphthene of the present invention and pyrazine class dyestuff is simple, and raw material is easy to get, and it is synthetic to be undertaken by following reaction formula:
Reaction formula when A, B are carboxyl:
The synthetic of dyestuff at first is that HX replaces bromine under palladium catalysis then at 5 bromos that have on the acenaphthenequinone ring of different substituents.When m=0, two carbonyls and Diaminomaleonitrile on the acenaphthenequinone ring carry out condensation, when m=1, are the two carbonyls and 4 on the acenaphthenequinone ring, and 5-diamino phthalonitrile carries out condensation, and cyano group is hydrolyzed in aqueous sodium hydroxide solution, can obtain acenaphthene and pyrazine dyestuff.
One is carboxyl in A, B, and when another was hydrogen or carboxyl, synthetic method was identical when being carboxyl with A, B.
Acenaphthene and the application of pyrazine dyestuff in dye sensitization solar battery comprise that structure, preparation process and the battery performance test of dye sensitization solar battery is:
(1) structure of dye sensitization solar battery:
Dye sensitization solar battery mainly is made up of light anode, photocathode and their substrate and ionogen; The material of light anode and photocathode substrate is a conductive glass, is covered with the transparent plastics of conducting film above; Photo-anode substrate work area one side is provided with nanoporous TiO
2Film, and be impregnated with acenaphthene and pyrazine class dyestuff; Photocathode substrate work area one side is provided with catalyst layer; Light anode and photocathode relative spacing are provided with, and periphery forms airtight cavity with the sealing material sealing, is filled with ionogen in the cavity;
(2) preparation process of dye sensitization solar battery:
A. the pre-treatment of conductive glass: conductive glass is fully cleaned successively dry for standby in removers, dehydrated alcohol and deionized water with ultrasonic wave;
B. the preparation of dye solution: the volume ratio that acenaphthene and pyrazine dyestuff are dissolved in the acetonitrile and the trimethyl carbinol is 1: 1 a mixed solvent, is mixed with 5 * 10
-4Mol/L solution;
C. the preparation of electrolyte solution: contain 0.6M tetrabutylammonium iodide, 0.1M LiI, 0.05MI with the preparation of absolutely dry acetonitrile
2With the solution of 0.5M to tert .-butylpyridine.
D. light anodic preparation:, prepare nanoporous TiO by silk screen printing through on the pretreated photo-anode substrate
2Thin-film material, and 450 ℃ of maintenance slowly coolings after 30 minutes down;
E. light anodic sensitization: at room temperature with nanoporous TiO
2Thin film layer is immersed in acenaphthene and the pyrazine dye solution, floods 24 hours, obtains the light anode of even absorbing dye through sensitization;
F. the preparation of photocathode:, plate metal Pt by thermal decomposition method and make catalyzer through on the pretreated photocathode substrate;
G. sealing: at the peripheral position of electrode, sealing material is evenly placed desired location, again two electrode base boards are closed and seal by printing, spraying or extruding;
H. above-mentioned ionogen is injected by vacuum or manual method, sealing makes dye sensitization solar battery.
(3) battery performance test: draw lead respectively from the light anode and the photocathode of battery, receive on the battery performance test device, the working area of battery is 0.2cm
2, use the solar simulator simulated solar irradiation, light intensity is adjusted to 100mW/cm
2The electricity conversion that records is 0.94～3.68%, and short-circuit current is 2.87～8.58mA/cm
2, open circuit voltage is 0.524～0.703mV, packing factor is 0.623～0.704.
Description of drawings
Fig. 1, Fig. 2, Fig. 3 and Fig. 4 are to be 100mW/cm in light intensity
2Simulated solar irradiation under, the discharge curve of dye sensitization solar battery.What X-coordinate was represented is voltage, and unit is a volt, and what ordinate zou was represented is current density, and unit is every square centimeter of a milliampere.Wherein: the N719 that Fig. 1 provides for the SolarOnix company with Switzerland is a light-sensitive coloring agent, and is assembled into the discharge curve that battery obtains according to the preparation process of dye sensitization solar battery; Fig. 2 is for being light-sensitive coloring agent with synthetic dyestuff in embodiment 1,2 and 3, and is assembled into the discharge curve that battery obtains according to the preparation process of dye sensitization solar battery; Fig. 3 is for being light-sensitive coloring agent with synthetic dyestuff in embodiment 4,5 and 6, and is assembled into the discharge curve that battery obtains according to the preparation process of dye sensitization solar battery; Fig. 4 is for being light-sensitive coloring agent with synthetic dyestuff in embodiment 7,8 and 9, and is assembled into the discharge curve that battery obtains according to the preparation process of dye sensitization solar battery.
Embodiment
Embodiment 1:3-pentanoic-8,9-dicarboxyl-acenaphthene and pyrazine synthetic
(1) 5-bromine acenaphthenequinone is synthetic:
In two mouthfuls of flasks of 500mL, add 20g (109.8mmol) acenaphthenequinone and 25.0mL liquid bromine (466.8mmol), begin to stir, temperature control is 6070 ℃ in the oil bath, and reaction solution is refluxed, and behind the 2h, stopped reaction adds aqueous solution of sodium bisulfite, is colourless to reaction solution.Behind the thin up, decompress filter, and repeatedly wash making beating with water, to pH=7.0.Filter cake recrystallization in Glacial acetic acid gets 5-bromine acenaphthenequinone, pale brown look needle-like crystal, yield 90% four times.Nuclear-magnetism
1H NMR (400MHz, DMSO-d
6) δ 8.39 (d, 1H), 8.21 (d, 1H), 8.15 (d, 1H), 8.04 (t, 1H), 7.96 (d, 1H); HRMS-EI (70eV) m/z.
(2) 5-pentanoic-acenaphthenequinone is synthetic:
This is reflected under the anhydrous and oxygen-free condition and carries out.
In two mouthfuls of flasks of exsiccant 250mL, add 1000mg (3.84mmol) 5-bromine acenaphthenequinone respectively, 650mg (3.84mmol) pentanoic, 10mgPd (OAc)
2(0.038mmol), 520mg potassium tert.-butoxide (4.6mmol), 30mg three tertiary butyl phosphorus a tetrafluoro borates (0.1mmol) add 150mL exsiccant toluene then, begin under the argon shield to stir, temperature control is 80 ℃ in the oil bath, react follow the tracks of no raw material to TLC till.Stopped reaction, cooling is filtered, and filtrate is washed after adding diethyl ether and diluting, salt is washed, anhydrous MgSO4 drying.Solvent steams with Rotary Evaporators and obtains the brownish black solid, uses methylene dichloride: the solution of sherwood oil=2: 1 (volume ratio) is that eluent separates purification on silicagel column, obtains 5-(pentanoic) acenaphthenequinone 353mg (1.01mmol), yield 26.4%.Nuclear-magnetism
1H NMR (400MHz, CDCl
3): δ 7.06-7.09 (m, 4H), 7.12-7.16 (m 2H), 7.28-7.32 (m, 4H), 7.36 (d, 1H), 7.47 (t, 1H), 7.72 (d, 1H), 7.96 (d, 1H), 8.01 (d, 1H) .FAB MS:m/e 349 (M
+).
(3) 3-pentanoic-8,9-dicyano-acenaphthene and pyrazine synthetic
In 25mL single port flask; add 400mg (1.146mmol) 5-pentanoic-acenaphthenequinone; 124mg (1.146mmol) Diaminomaleonitrile; 10mL exsiccant propyl carbinol; be heated with stirring to back flow reaction under the nitrogen protection; stopped reaction behind the 4h, the cooling back adds the methylene dichloride dilute reaction solution, and organic phase washes with water, salt is washed, anhydrous MgSO4 drying.Solvent steams with Rotary Evaporators and obtains the reddish black solid, use methylene dichloride: the solution of sherwood oil=2: 1 (volume ratio) is that eluent separates purification on silicagel column, obtain 3-pentanoic-8,9-dicyano-acenaphthene and pyrazine 325mg (0.772mmol), yield 88.5%.Nuclear-magnetism
1HNMR (CDCl
3): δ 7.13-7.18 (m, 6H), 7.29-7.34 (m, 4H), 7.37 (d, 1H), 7.56 (t, 1H), 7.85 (d, 1H), 8.27 (d, 1H), 8.38 (d, 1H) .FAB MS:m/e 421 (M
+).
(4) 3-pentanoic-8,9-dicarboxyl-acenaphthene and pyrazine synthetic
In 100mL single port flask, add 325mg (0.772mmol) 3-pentanoic-8,9-dicyano-acenaphthene and pyrazine, the aqueous sodium hydroxide solution 60mL that adds 4M, begin to stir, temperature control to 90 ℃ in the oil bath, stopped reaction behind the reaction 48h, cooling afterreaction liquid thin up, filtration, filter cake washs two to three times with ether, obtain orange solids, again this solid suspension is carried out acidifying in dilute hydrochloric acid solution, filter after drying, obtain 3-pentanoic-8,9-dicarboxyl-acenaphthene and pyrazine, garnet solid, yield 70.6%.Nuclear-magnetism
1HNMR (DMSO-d
6): δ 7.09-7.15 (m, 6H), 7.30-7.40 (m, 5H), 7.70 (t, 1H), 7.81 (d, 1H), 8.36 (d, 2H) .MS API-ES:[M-H]
+(458, M/Z).
Embodiment 2:3-pentanoic-8,9-dicarboxyl-acenaphthene and pyrazine acene synthetic
(1) 3-pentanoic-8,9-dicyano-acenaphthene and pyrazine acene synthetic
(3) among synthetic method and the embodiment 1 are basic identical, nuclear-magnetism
1HNMR ((CDCl
3)): δ 7.12-7.16 (m, 6H), 7.32 (t, 4H), 7.46 (d, 1H), 7.62 (t, 1H), 7.86 (d, 1H), 8.36 (d, 1H), 8.42 (d, 1H), 8.60 (d, 2H) .FAB MS:m/e 471 (M
+).
(2) 3-pentanoic-8,9-dicarboxyl-acenaphthene and pyrazine acene synthetic
(4) among synthetic method and the embodiment 1 are basic identical, nuclear-magnetism
1HNMR ((DMSO-d
6)): δ 7.09-7.14 (m, 6H), 7.35 (t, 4H), 7.44 (d, 1H), 7.30 (t, 1H), 7.80 (d, 1H), 8.38-8.41 (m, 4H) .MS API-ES:[M-H]
+(508, M/Z).
Synthesizing of embodiment 3:3-pentanoic-8-carboxyl-acenaphthene and pyrazine acene and 3-pentanoic-9-carboxyl-acenaphthene and pyrazine acene
(1) 3-pentanoic-8-cyano group-acenaphthene and pyrazine acene and 3-pentanoic-9-cyano group-acenaphthene and pyrazine acene is synthetic
(3) among synthetic method and the embodiment 1 are basic identical, and the isomers for 3-pentanoic-8-cyano group-acenaphthene and pyrazine acene and 3-pentanoic-9-cyano group-acenaphthene and pyrazine acene that this reaction obtains can't separate isomers by silicagel column, passes through nuclear-magnetism
1HNMR learns that the isomers ratio is about 1: 1.Nuclear-magnetism
1HNMR (CDCl
3): δ 7.10-7.16 (m, 6H), 7.28-7.32 (m, 4H), 7.45-7.48 (m, 1H), 7.59 (t, 1H), 7.83 (d, 1H), 7.86-7.90 (m, 1H), 8.25-8.28 (m, 1H), 8.34-8.39 (m, 2H), 8.54 (s, 1H) .FAB MS:m/e 446 (M
+).
(2) 3-pentanoic-8-carboxyl-acenaphthene and pyrazine acene and 3-pentanoic-9-carboxyl-acenaphthene and pyrazine acene is synthetic
(4) among synthetic method and the embodiment 1 are basic identical, and the isomers for 3-pentanoic-8-carboxyl-acenaphthene and pyrazine acene and 3-pentanoic-9-carboxyl-acenaphthene and pyrazine acene that this reaction obtains can't separate isomers by silicagel column, passes through nuclear-magnetism
1HNMR learns that the isomers ratio is about 1: 1.Nuclear-magnetism
1HNMR (DMSO-d
6): δ 7.10-7.14 (m, 6H), 7.34-7.38 (m, 4H), 7.44-7.47 (m, 1H), 7.71-7.82 (m, 2H), 8.26 (d, 2H), 8.39-8.42 (m, 2H), 8.70 (m, 1H) .MS API-ES:[M-H]
+(464, M/Z).
Embodiment 4:3-(N-butyl)-aniline-8,9-dicarboxyl-acenaphthene and pyrazine synthetic
(1) 5-(N-butyl)-aniline-acenaphthenequinone is synthetic
(2) among synthetic method and the embodiment 1 are basic identical, nuclear-magnetism
1HNMR ((CDCl
3)): δ 7.0 (d, 2H), 7.08 (t, 1H), 7.26-7.31 (m, 2H), 7.41 (t, 1H), 7.46 (d, 1H), 7.58 (d, 1H), 7.9 (d, 1H), 8.14 (d, 1H), 4.04 (t, 2H), 1.73-1.79 (m, 2H), 1.41-1.46 (m, 2H), 0.96 (t, 3H) .MS APCI:[M+H]
+(330, M/Z).
(2) 3-(N-butyl)-aniline-8,9-dicyano-acenaphthene and pyrazine synthetic
(3) among synthetic method and the embodiment 1 are basic identical, nuclear-magnetism
1HNMR (CDCl
3): δ 7.12-7.16 (m, 3H), 7.32-7.36 (t, 2H), 7.34 (d, 1H), 7.49 (t, 1H), 7.68 (d, 1H), 8.37 (d, 1H), 8.42 (d, 1H), 4.05 (t, 2H), 1.81 (m, 2H), 1.43-1.47 (m, 2H), 0.97 (t, 3H) .FAB MS:m/e 401 (M
+).
(3) 3-(N-butyl)-aniline-8,9-dicarboxyl-acenaphthene and pyrazine synthetic
(4) among synthetic method and the embodiment 1 are basic identical, nuclear-magnetism
1HNMR (DMSO-d
6): δ 6.93-6.98 (m, 3H), 7.26 (t, 2H), 7.65-7.67 (m, 2H), 7.31 (d, 1H), 8.34 (d, 1H), 8.43 (d, 1H), 4.01 (t, 2H), 1.70 (m, 2H), 1.37-1.42 (m, 2H), 0.89 (t, 3H) .MS API-ES:[M-H]
+(438, M/Z).
Embodiment 5:3-(N-butyl)-aniline-8,9-dicarboxyl-acenaphthene and pyrazine acene synthetic
(1) 3-(N-butyl)-aniline-8,9-dicyano-acenaphthene and pyrazine acene synthetic
(3) among synthetic method and the embodiment 1 are basic identical, nuclear-magnetism
1HNMR (CDCl
3): δ 7.05-7.11 (m, 3H), 7.30-7.34 (t, 2H), 7.54-7.58 (t, 2H), 7.70 (d, 1H), 8.40 (d, 1H), 8.59 (d, 2H), 8.66 (s, 1H), 4.06 (t, 2H), 1.82-1.84 (m, 2H), 1.41-1.48 (m, 2H), 0.97 (t, 3H) .FAB MS:m/e 451 (M
+).
(2) 3-(N-butyl)-aniline-8,9-dicarboxyl-acenaphthene and pyrazine acene synthetic
(4) among synthetic method and the embodiment 1 are basic identical, nuclear-magnetism
1HNMR (DMSO-d
6): δ 6.90-6.94 (m, 3H), 7.25 (t, 2H), 7.69-7.75 (m, 3H), 8.38 (d, 2H), 8.45-8.47 (m, 1H), 4.02 (t, 2H), 1.69-1.70 (m, 2H), 1.37-1.43 (m, 2H), 0.89 (t, 3H) .MS API-ES:[M-H]
+(488, M/Z).
Synthesizing of embodiment 6:3-(N-butyl)-aniline-8-carboxyl-acenaphthene and pyrazine acene and 3-(N-butyl)-aniline-9-carboxyl-acenaphthene and pyrazine acene
(1) 3-(N-butyl)-aniline-8-cyano group-acenaphthene and pyrazine acene and 3-(N-butyl)-aniline-9-cyano group-acenaphthene and pyrazine acene is synthetic
(3) among synthetic method and the embodiment 1 are basic identical, the isomers that this reaction obtains for 3-(N-butyl)-aniline-8-cyano group-acenaphthene and pyrazine acene and 3-(N-butyl)-aniline-9-cyano group-acenaphthene and pyrazine acene, isomers can't be separated by silicagel column, pass through nuclear-magnetism
1HNMR learns that the isomers ratio is about 1: 1.Nuclear-magnetism
1HNMR (CDCl
3): δ 6.94-7.03 (m, 3H), 7.24-7.30 (m, 2H), 7.55-7.91 (m, 4H), 8.24-8.39 (m, 2H), 8.48-8.60 (m, 2H), 4.0-4.04 (m, 2H), 1.68-1.82 (m, 2H), 1.42-1.49 (m, 2H), 0.96-0.98 (m, 3H) .FAB MS:m/e 426 (M
+).
(2) 3-(N-butyl)-aniline-8-carboxyl-acenaphthene and pyrazine acene and 3-(N-butyl)-aniline-9-carboxyl-acenaphthene and pyrazine acene is synthetic
(4) among synthetic method and the embodiment 1 are basic identical, the isomers for 3-(N-butyl)-aniline-8-carboxyl-acenaphthene and pyrazine acene and 3-(N-butyl)-aniline-9-carboxyl-acenaphthene and pyrazine acene that this reaction obtains.Nuclear-magnetism
1HNMR (DMSO-d
6): δ 6.93 (m, 3H), 7.25 (t, 2H), 7.67 (m, 3H), 8.23-8.38 (m, 4H), 8.66 (d, 1H), 4.01 (t, 2H), 1.70 (m, 2H), 1.40 (m, 2H), 0.90 (t, 3H) .MS API-ES:[M-H]
+(444, M/Z).
Embodiment 7:3-(N-methyl)-aniline-8,9-dicarboxyl-acenaphthene and pyrazine synthetic
(1) 5-(N-methyl)-aniline-acenaphthenequinone is synthetic
(2) among synthetic method and the embodiment 1 are basic identical, nuclear-magnetism
1HNMR (CDCl
3): δ 7.04-7.06 (d, 2H), 7.11 (t, 1H), 7.30-7.34 (t, 2H), 7.42-7.46 (t, 2H), 7.63 (d, 1H), 7.93 (d, 1H), 8.15 (d, 1H), 3.63 (s, 3H) .MSAPCI:[M+H]
+(288, M/Z).
(2) 3-(N-methyl)-aniline-8,9-dicyano-acenaphthene and pyrazine synthetic
(3) among synthetic method and the embodiment 1 are basic identical, nuclear-magnetism
1HNMR (CDCl
3): δ 7.0-7.07 (m, 3H), 7.32-7.41 (m, 3H), 7.49 (t, 1H), 7.50-7.53 (t, 1H), 7.71-7.3 (d, 1H), 8.33-8.35 (d, 1H), 8.38-8.41 (d, 1H), 3.67 (s, 3H) .FAB MS:m/e 359 (M
+).
(3) 3-(N-methyl)-aniline-8,9-dicarboxyl-acenaphthene and pyrazine synthetic
(4) among synthetic method and the embodiment 1 are basic identical, nuclear-magnetism
1HNMR (DMSO-d
6): δ 7.18-7.20 (m, 3H), 7.27-7.31 (t, 3H), 7.59 (d, 1H), 7.65-7.69 (t, 1H), 7.76-7.78 (d, 1H), 8.34-8.36 (d, 1H), 8.42-8.44 (d, 1H), 3.57 (s, 3H) .MS API-ES:[M-H]
+(396, M/Z).
Embodiment 8:3-(N-methyl)-aniline-8,9-dicarboxyl-acenaphthene and pyrazine acene synthetic
(1) 3-(N-methyl)-aniline-8,9-dicyano-acenaphthene and pyrazine acene synthetic
(3) among synthetic method and the embodiment 1 are basic identical, nuclear-magnetism
1HNMR (CDCl
3): δ 7.10-7.12 (m, 3H), 7.31-7.35 (t, 2H), 7.51-7.54 (d, 1H), 7.58-7.52 (t, 1H), 7.78-7.80 (d, 1H), 8.40-8.42 (d, 1H), 8.50-8.52 (d, 1H), 8.56-8.58 (d, 2H), 3.67 (s, 3H) .FAB MS:m/e 409 (M
+).
(2) 3-(N-methyl)-aniline-8,9-dicarboxyl-acenaphthene and pyrazine acene synthetic
(4) among synthetic method and the embodiment 1 are basic identical, nuclear-magnetism
1HNMR (DMSO-d
6): δ 6.94-7.02 (m, 3H), 7.26-7.30 (t, 2H), 7.64-7.66 (d, 1H), 7.69-7.73 (t, 1H), 7.76-7.78 (d, 1H), 8.38-8.40 (d, 1H), 8.45-8.47 (d, 1H), 8.94-8.95 (d, 1H), 3.57 (s, 3H) .MS API-ES:[M-H]
+(446, M/Z).
Synthesizing of embodiment 9:3-(N-methyl)-aniline-8-carboxyl-acenaphthene and pyrazine acene and 3-(N-methyl)-aniline-9-carboxyl-acenaphthene and pyrazine acene
(1) 3-(N-methyl)-aniline-8-cyano group-acenaphthene and pyrazine acene and 3-(N-methyl)-aniline-9-cyano group-acenaphthene and pyrazine acene is synthetic
(3) among synthetic method and the embodiment 1 are basic identical, the isomers that this reaction obtains for 3-(N-methyl)-aniline-8-cyano group-acenaphthene and pyrazine acene and 3-(N-methyl)-aniline-9-cyano group-acenaphthene and pyrazine acene, isomers can't be separated by silicagel column, pass through nuclear-magnetism
1HNMR learns that the isomers ratio is about 2.5: 1.Nuclear-magnetism
1HNMR (CDCl
3): δ 7.08-7.10 (m, 3H), 7.31-7.35 (m, 2H), 7.51-7.53 (m, 1H), 7.73-7.75 (d, 1H), 7.92-7.93 (m, 1H), 8.40-8.42 (d, 2H), 8.56-8.60 (d, 2H), 8.68-8.70 (d, 1H), 3.66 (s, 3H) .FAB MS:m/e 384 (M
+).
(2) 3-(N-methyl)-aniline-8-carboxyl-acenaphthene and pyrazine acene and 3-(N-methyl)-aniline-9-carboxyl-acenaphthene and pyrazine acene is synthetic
(4) among synthetic method and the embodiment 1 are basic identical, the isomers for 3-(N-methyl)-aniline-8-carboxyl-acenaphthene and pyrazine acene and 3-(N-methyl)-aniline-9-carboxyl-acenaphthene and pyrazine acene that this reaction obtains.Nuclear-magnetism
1HNMR (DMSO-d
6): δ 6.97-7.03 (m, 3H), 7.26-7.30 (t, 2H), 7.65-7.78 (m, 3H), 8.26 (m, 2H), 8.38-8.40 (d, 1H), 8.45-8.47 (d, 1H), 8.69 (s, 3H), 3.58 (s, 3H) .MS API-ES:[M-H]
+(402, M/Z).
Comparative Examples: the N719 that provides with the SolarOnix company of Switzerland is a light-sensitive coloring agent
Embodiment 10:
The concrete preparation process of dye sensitization solar battery is as follows:
(1) pre-treatment of conductive glass: conductive glass is fully cleaned successively dry for standby in removers, dehydrated alcohol and deionized water with ultrasonic wave;
(2) preparation of dye solution: the volume ratio that the N719 dyestuff is dissolved in the acetonitrile and the trimethyl carbinol is 1: 1 a mixed solvent, is mixed with 5 * 10
-4Mol/L solution;
(3) preparation of electrolyte solution: contain 0.6M tetrabutylammonium iodide, 0.1M LiI, 0.05M I with the preparation of absolutely dry acetonitrile
2With the solution of 0.5M to tert .-butylpyridine.
(4) light anodic preparation:, prepare nanoporous TiO by silk screen printing through on the pretreated photo-anode substrate
2Thin-film material, and 450 ℃ of maintenance slowly coolings after 30 minutes down;
(5) light anodic sensitization: at room temperature with nanoporous TiO
2Thin film layer is immersed in the N719 dye solution, floods 24 hours, obtains the light anode of even absorbing dye through sensitization;
(6) preparation of photocathode:, plate metal Pt by thermal decomposition method and make catalyzer through on the pretreated photocathode substrate;
(7) sealing: at the peripheral position of electrode, sealing material is evenly placed desired location, again two electrode base boards are closed and seal by printing, spraying or extruding;
(8) above-mentioned ionogen is injected by vacuum or manual method, sealing makes dye sensitization solar battery.
Embodiment 11:
The test of dye sensitization solar battery performance:
Will be according to the cell preparation step among the embodiment 10, be that the battery of sensitizing dye assembling is drawn lead respectively from light anode and photocathode with N719, to receive on the battery performance test device, the working area of battery is 0.2cm
2, use the solar simulator simulated solar irradiation, light intensity is adjusted to 100mW/cm
2The electricity conversion that records is 5.91%, and short-circuit current is 14.45mA/cm
2, open circuit voltage is 0.696mV, packing factor is 0.587; The battery discharge curve that records as shown in Figure 1.
Embodiment 12:
With synthetic compound among the embodiment 1 to 9 as sensitizing dye, according to the cell preparation step among the embodiment 10, be assembled into battery, then according to the performance of embodiment 11 test dye sensitization solar batteries, the electricity conversion that records is 0.94～3.68%, and short-circuit current is 2.87～8.58mA/cm
2, open circuit voltage is 0.524～0.703mV, and packing factor is 0.623～0.704, and the battery discharge curve that records as Fig. 2, Fig. 3 and shown in Figure 4, is summarized in the data of gained in the table 1:
The dyestuff of table 1 Comparative Examples and embodiment 1-9 is used for the dye sensitization solar battery performance data
| Dyestuff | Short-circuit current (mA/cm 2) | Open circuit voltage (mV) | Packing factor | Electricity conversion (%) |
| N719 | 14.45 | 0.696 | 0.587 | 5.91 |
| |
8.58 | 0.649 | 0.661 | 3.68 |
| |
6.34 | 0.54 | 0.633 | 2.20 |
| |
7.05 | 0.614 | 0.678 | 2.93 |
| |
5.45 | 0.703 | 0.74 | 2.84 |
| |
4.18 | 0.554 | 0.682 | 1.58 |
| |
4.38 | 0.591 | 0.687 | 1.78 |
| |
4.82 | 0.669 | 0.704 | 2.27 |
| |
4.15 | 0.557 | 0.67 | 1.55 |
| |
2.87 | 0.524 | 0.623 | 0.94 |
Claims (2)
1. a class is used for the acenaphthene and the pyrazine dyestuff of dye sensitization solar battery, it is characterized in that having following general structure:
Wherein, m is 0～1 integer; Among A, the B one when being carboxyl, another is hydrogen or carboxyl;
In the formula: X
1Be C
1～C
4Straight chained alkyl.
2. according to the described purposes that is used for the acenaphthene and the pyrazine dyestuff of dye sensitization solar battery of claim 1, it is characterized in that structure, preparation process and the battery performance test of dye sensitization solar battery is:
(1) structure of dye sensitization solar battery:
Dye sensitization solar battery mainly is made up of light anode, photocathode and their substrate and ionogen; The material of light anode and photocathode substrate is conductive glass, be covered with the transparent plastics of conducting film; Photo-anode substrate work area one side is provided with nanoporous TiO
2Film, and be impregnated with acenaphthene and pyrazine dyestuff; Photocathode substrate work area one side is provided with catalyst layer; Light anode and photocathode relative spacing are provided with, and periphery forms airtight cavity with the sealing material sealing, is filled with ionogen in the cavity;
(2) preparation process of dye sensitization solar battery:
A. the pre-treatment of conductive glass: conductive glass is fully cleaned successively dry for standby in removers, dehydrated alcohol and deionized water with ultrasonic wave;
B. the preparation of dye solution: the volume ratio that the described acenaphthene of claim 1 and pyrazine dyestuff are dissolved in the acetonitrile and the trimethyl carbinol is 1: 1 a mixed solvent, is mixed with 5 * 10
-4Mol/L solution;
C. the preparation of electrolyte solution: contain 0.6M tetrabutylammonium iodide, 0.1M LiI, 0.05M I with the preparation of absolutely dry acetonitrile
2With the solution of 0.5M to tert .-butylpyridine;
D. light anodic preparation: on the pretreated photo-anode substrate of process, preparing area by silk screen printing is 0.2cm
2, thickness is the nanoporous TiO of 18～20 μ m
2Thin-film material, and 450 ℃ of maintenance slowly coolings after 30 minutes down;
E. light anodic sensitization: at room temperature with nanoporous TiO
2Thin film layer is immersed in described acenaphthene of claim 1 and the pyrazine dye solution, floods 24 hours, obtains the light anode of even absorbing dye through sensitization;
F. the preparation of photocathode:, plate Pt by thermal decomposition method and do catalyst layer through on the pretreated photocathode substrate;
G. sealing: at the peripheral position of electrode, sealing material is evenly placed desired location, again two electrode base boards are closed and seal by printing, spraying or extruding;
H. above-mentioned ionogen is injected by vacuum or manual method, sealing makes dye sensitization solar battery;
(3) battery performance test: draw lead respectively from the light anode and the photocathode of battery, receive on the battery performance test device, the working area of battery is 0.2cm
2, use the solar simulator simulated solar irradiation, light intensity is adjusted to 100mW/cm
2The electricity conversion that records is 0.94～3.68%, and short-circuit current is 2.87～8.58mA/cm
2, open circuit voltage is 0.524～0.703mV, packing factor is 0.623～0.704.
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