CN102617832B - Poly triphenylamine organic electron hole transmission material for carbohydrate modification of full-solid-state quantum dot sensitized solar cell - Google Patents
Poly triphenylamine organic electron hole transmission material for carbohydrate modification of full-solid-state quantum dot sensitized solar cell Download PDFInfo
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Abstract
The invention discloses a poly triphenylamine organic electron hole transmission material for carbohydrate modification of full-solid-state quantum dot sensitized solar cells, which is characterized in that the organic electron hole transmission material uses poly triphenylamine as a matrix, carbohydrate is introduced to the position a of the poly triphenylamine to perform modification, the polymerization degree n of the poly triphenylamine matrix is one of the numerical value range of 20-50, the carbohydrate can be one of glyceraldehydes, erythrose, threose, ribose, arabinose, xylose, lyxose, allose, altrose, glucose, mannose, gulose, idose, galactose and talose.
Description
[technical field]: the invention belongs to technical field of solar batteries, especially relate to the application of poly-triphenylamine organic hole transport material in all solid state quantum dot sensitized solar cell that a class carbohydrate is modified.
[background technology]: the problem that volatilization is revealed, had a strong impact on the stability of battery, be difficult to meet the needs of practical application.Adopt the organic hole transport material to replace liquid electrolyte can be assembled into all solid state quantum dot sensitized solar cell, can solve the volatilization leakage problem of liquid electrolyte.The organic hole transport material of report only has mono-kind of spiro-OMeDAT at present, also from dye sensitization solar battery, lending, be not well positioned to meet the needs of quantum dot sensitized solar cell, so efficiency very low (being far smaller than 1%), organic hole transport material ionogen also is not developed out efficiently.
Organic hole transport material for quantum dot sensitized solar cell should have: the hole mobility that (1) is higher; (2) contact between the titanium dioxide film of organic hole transport material and porous will be got well; 3) electronics and the dark reaction between the hole in hole mobile material that are injected in titanium dioxide film are little.Triphenylamine, as the p-N-type semiconductorN, has higher hole mobility, and, by the triphenylamine polymerization, makes poly-triphenylamine, can make hole fast transferring in molecule, further improves the mobility in hole, is a very potential class organic hole transport material.The electronics and the dark reaction between the hole in hole mobile material that how to improve the contact of poly-triphenylamine molecule and poriferous titanium dioxide film and suppress in titanium dioxide film are the problems of needing solution badly.
Based on this, this patent has been introduced saccharide compound on the poly-triphenylamine parent, utilize hydroxyl and the effect of poriferous titanium dioxide film on sugar, make this sugar-modified poly-triphenylamine can be adsorbed on preferably on the poriferous titanium dioxide film, increased the contact of itself and poriferous titanium dioxide film, and suppressed dark reaction, obtained good effect.Patent and the document announced are retrieved, do not found associated viscera.Patent of the present invention has obvious practicality, novelty and novelty.
[summary of the invention]: the present invention takes full advantage of hydroxyl can adsorb on titanium dioxide film characteristic, utilize saccharide compound to modify poly-triphenylamine, thereby obtained the derivative of a series of poly-triphenylamines, and it is used in quantum dot sensitized solar cell, obtained good effect.Utilizing the interactional concept of organic macromolecule and inorganic semiconductor to design quantum dot sensitization solar battery electrolyte is the place of the new meaning of this invention.In addition, a series of poly-triphenylamine derivatives that prepare in patent of the present invention are as the organic hole transport material, to be applied in all solid state quantum dot sensitized solar cell for the first time, and result is compared and also had advance with existing result.
[technical scheme of the present invention]:
On the surface of titanium dioxide nano material, exist a large amount of hydroxyls, therefore can with sugar in hydroxyl form hydrogen bond; The surface of titanium dioxide nano material also has the undersaturated titanium atom of a large amount of coordinations in addition, they be very easy to and sugared hydroxyl in the oxygen combination, form coordinate bond.This hydrogen bond and coordinate bond acting in conjunction, can make the contact performance between the titanium dioxide film of sugar-modified poly-triphenylamine and porous greatly improve, and is conducive to improve the performance of battery.On the other hand, the dark reaction between the electronics of injection titanium dioxide and the hole of hole mobile material is undertaken by the undersaturated titanium atom of coordination, and this coordination can reduce the number of surface state greatly, suppresses the generation of dark reaction.
The synthetic schemes of described poly-triphenylamine organic hole transport material: the carbohydrate that this patent adopts is poly-hydroxy aldehyde, be in molecule, to contain great amount of hydroxy group, end at molecule has aldehyde radical simultaneously, utilize the Wittig reaction of the phosphorus ylide reagent (2) of aldehyde radical and poly-triphenylamine base, by two keys, corresponding carbohydrate is incorporated on poly-triphenylamine.Therefore, the synthetic the first step is the phosphorus ylide reagent (2) for preparing the poly-triphenylamine base.
Phosphorus ylide reagent (2) preparation process of poly-triphenylamine base: poly-triphenylamine (1) and triphenyl phosphorus that iodomethyl is replaced react; obtain quaternary alkylphosphonium salt, the quaternary alkylphosphonium salt that then will obtain and highly basic react the phosphorus ylide reagent (2) that obtains corresponding poly-triphenylamine base under nitrogen protection.Any one reaction by the phosphorus ylide reagent (2) of the poly-triphenylamine base that obtains and corresponding Glycerose, erythrose, threose, ribose, pectinose, wood sugar, Lay threose, allose, altrose, glucose, seminose, gulose, idose, semi-lactosi and talose, just obtained corresponding sugar-modified poly-triphenylamine (3).
The assembling process of described all solid state quantum dot sensitized solar cell is as follows:
1) adopt the method for silk screen printing that titania slurry is printed on conductive glass (4), number of times by printing is controlled thickness, by printed titanium dioxide film high-temperature calcination, to remove the organism in slurry, and improve the contact tightness degree between titania nanoparticles; 2) titanium dioxide film (5) after the calcining immerses the aqueous solution of halfcystine, then with acetone, clean, finally put into the toluene solution of CdSe quantum dot, CdSe quantum dot (6) is adsorbed on titanium dioxide electrodes and obtains the light anode, the organic hole transport material (7) that 3) will synthesize is dissolved in volatile acetonitrile, methylene dichloride, any one solvent of ethanol, and concentration is 0.01～0.5mol/L; 4) above-mentioned solution is dripped on the light anode with the method for spin coating, in order to organic hole transport material solution is better immersed in the light anode, and the volatilization of accelerated solvent; 5) containing steaming gold on the light anode of organic hole transport material, as to electrode (8), obtain complete all solid state quantum dot sensitized solar cell.
The all solid state quantum dot sensitized solar cell of described material assembling reached～electricity conversion of 1-2%.
The poly-triphenylamine organic hole transport material that a described class is modified for the carbohydrate of all solid state quantum dot sensitized solar cell, it is characterized in that described organic hole transport material is take poly-triphenylamine as parent, in a position of poly-triphenylamine group, introduce saccharide compound and modify.
The poly-triphenylamine organic hole transport material that a described class is modified for the carbohydrate of all solid state quantum dot sensitized solar cell, the value that it is characterized in that the polymerization degree n of described poly-triphenylamine parent is arbitrary numerical value of 20-50.
The poly-triphenylamine organic hole transport material that a described class is modified for the carbohydrate of all solid state quantum dot sensitized solar cell, is characterized in that described saccharide compound can be any one of Glycerose, erythrose, threose, ribose, pectinose, wood sugar, Lay threose, allose, altrose, glucose, seminose, gulose, idose, semi-lactosi and talose.
The poly-triphenylamine organic hole transport material that a described class is modified for the carbohydrate of all solid state quantum dot sensitized solar cell, it is characterized in that quantum dot sensitized solar cell is to assemble by following step: at first the organic hole transport material is dissolved in acetonitrile, methylene dichloride, any one solvent of ethanol, is made into the dilute solution that concentration is 0.01～0.5mol/L; Then the method by spin coating drips in the light anode of quantum dot sensitized solar cell, allows solvent evaporates; Finally gold is evaporated on the above-mentioned light anode that contains the organic hole transport material electrode.
[advantage of the present invention and effect]: the poly-triphenylamine organic hole transport material that patent of the present invention provides a class to modify for the carbohydrate of all solid state quantum dot sensitized solar cell, it has the following advantages and beneficial effect: 1) triphenylamine is as the p-N-type semiconductorN, has higher hole mobility, and by the triphenylamine polymerization, make poly-triphenylamine, can make hole fast transferring in molecule, further improve the mobility in hole, be a very potential class organic hole transport material.2) this patent has been introduced saccharide compound on the poly-triphenylamine parent, utilize hydroxyl and the effect of poriferous titanium dioxide film on sugar, make this sugar-modified poly-triphenylamine can be adsorbed on preferably on the poriferous titanium dioxide film, increased the contact of itself and poriferous titanium dioxide film, and suppressed dark reaction, obtained good effect.
[accompanying drawing explanation]:
Fig. 1 is poly-triphenylamine base organic hole transport material building-up process.
Fig. 2 is based on the structural representation of all solid state quantum dot sensitized solar cell of organic hole transport material.
[embodiment]:
Below in conjunction with embodiment, content of the present invention is described further, but protection domain of the present invention is not limited only to following examples, everyly belongs to the technical scheme that content of the present invention is equal to, all belong to the protection domain of this patent.
The 20mmol triphenyl phosphorus is dissolved in the 200mL tetrahydrofuran (THF), then the 1mmol polymerization degree being about to the poly-triphenylamine (1) that 20 iodomethyl replaces drips slowly in above-mentioned solution, stirring at room 24 hours, wash the precipitation that obtains drying with ether.Then by dried dissolution of solid in the 200mL tetrahydrofuran (THF), under nitrogen protection, add the NaH of 40mmol, stirring at room 20 hours, obtain phosphorus ylide (2).Phosphorus ylide (2) 5mmol is dissolved in the 20mL tetrahydrofuran (THF), add any one of the corresponding Glycerose of 100mmol, erythrose, threose, ribose, pectinose, wood sugar, Lay threose, allose, altrose, glucose, seminose, gulose, idose, semi-lactosi and talose, stirring at room 48 hours.After reaction stops, reaction solution is poured into water to washing, and extracts organic product with anhydrous diethyl ether, the organic phase anhydrous sodium sulfate drying that obtains, rotary evaporation is except desolventizing.The solid that obtains carries out separating-purifying (take sherwood oil as eluent) with column chromatography, obtains pure sugar-modified poly-triphenylamine organic hole transport material (3), and productive rate is 45～56%.
The 50mmol triphenyl phosphorus is dissolved in the 200mL tetrahydrofuran (THF), then the 1mmol polymerization degree being about to the poly-triphenylamine (1) that 50 iodomethyl replaces drips slowly in above-mentioned solution, stirring at room 24 hours, wash the precipitation that obtains drying with ether.Then by dried dissolution of solid in the 200mL tetrahydrofuran (THF), under nitrogen protection, add the NaH of 80mmol, stirring at room 20 hours, obtain phosphorus ylide (2).Phosphorus ylide (2) 1mmol is dissolved in the 20mL tetrahydrofuran (THF), add any one of the corresponding Glycerose of 50mmol, erythrose, threose, ribose, pectinose, wood sugar, Lay threose, allose, altrose, glucose, seminose, gulose, idose, semi-lactosi and talose, stirring at room 48 hours.After reaction stops, reaction solution is poured into water to washing, and extracts organic product with anhydrous diethyl ether, the organic phase anhydrous sodium sulfate drying that obtains, rotary evaporation is except desolventizing.The solid that obtains carries out separating-purifying (take sherwood oil as eluent) with column chromatography, obtains pure sugar-modified poly-triphenylamine organic hole transport material (3), and productive rate is 58-62%.
The 35mmol triphenyl phosphorus is dissolved in the 200mL tetrahydrofuran (THF), then by the 1mmol polymerization degree, be to be about the poly-triphenylamine (1) that 35 iodomethyl replaces to drip slowly in above-mentioned solution, stirring at room 24 hours, wash the precipitation that obtains drying with ether.Then by dried dissolution of solid in the 200mL tetrahydrofuran (THF), under nitrogen protection, add the NaH of 70mmol, stirring at room 20 hours, obtain phosphorus ylide (2).Phosphorus ylide (2) 1mmol is dissolved in the 20mL tetrahydrofuran (THF), add any one of the corresponding Glycerose of 35mmol, erythrose, threose, ribose, pectinose, wood sugar, Lay threose, allose, altrose, glucose, seminose, gulose, idose, semi-lactosi and talose, stirring at room 48 hours.After reaction stops, reaction solution is poured into water to washing, and extracts organic product with anhydrous diethyl ether, the organic phase anhydrous sodium sulfate drying that obtains, rotary evaporation is except desolventizing.The solid that obtains carries out separating-purifying (take sherwood oil as eluent) with column chromatography, obtains pure sugar-modified poly-triphenylamine organic hole transport material (3), and productive rate is 52-67%.
The assembling of all solid state quantum dot sensitized solar cell:
1) adopt the method for silk screen printing that titania slurry is printed on to conductive glass (4) above, the formula of titania slurry is: 0.26g ethyl cellulose and 0.95g titania nanoparticles (P25) are dispersed in the 5mL Terpineol 350.Print 1 layer, obtain the titanium dioxide film of 2 micron thickness, 450 ℃ of printed titanium dioxide are calcined to half an hour, to remove the organism in slurry, and improve the contact tightness degree between titania nanoparticles; 2) titanium dioxide film for preparing (5) immerses the aqueous solution of halfcystine, under 70 ℃, places 1 hour, then with acetone, cleans.Finally put into the toluene solution of CdSe quantum dot, 24 hours, obtain the titanium dioxide electrodes of quantum dot (6) sensitization, i.e. the light anode; The organic hole transport material (7) that 3) will synthesize, the poly-triphenylamine of glucose modified, be dissolved in acetonitrile, and concentration is 0.25mol/L; 4) above-mentioned solution is dripped on the light anode with the method for spin coating, in order to organic hole transport material solution is better immersed in the light anode, and the volatilization of accelerated solvent; 5) treat that solvent evaporates does, steam gold containing on the light anode of organic hole transport material, as to electrode (8), the thickness of gold is 100nm, obtains complete all solid state quantum dot sensitized solar cell.The electricity conversion of battery is 1.7%.
Other organic hole transport material is done ionogen, and the process of all solid state quantum dot sensitized solar cell of assembling is identical with above-mentioned process, and corresponding efficiency sees the following form.
Sugar-modified poly-triphenylamine is assembled into the efficiency table of battery
| Efficiency | |
| Glycerose | 1.4％ |
| Erythrose | 1.1％ |
| Threose | 1.3％ |
| Ribose | 1.7％ |
| Pectinose | 1.4％ |
| Wood sugar | 1.9％ |
| The Lay threose | 1.8％ |
| Allose | 1.4％ |
| Altrose | 1.2％ |
| Glucose | 1.7％ |
| Seminose | 1.8％ |
| Gulose | 1.7％ |
| Idose | 1.1％ |
| Semi-lactosi | 1.5％ |
| Talose | 1.8％ |
Claims (3)
1. a class is for the poly-triphenylamine organic hole transport material of the carbohydrate modification of all solid state quantum dot sensitized solar cell, it is characterized in that described organic hole transport material is take poly-triphenylamine as parent, in a position of poly-triphenylamine group, introduce saccharide compound and modify; Described saccharide compound is any one of Glycerose, erythrose, threose, ribose, pectinose, wood sugar, Lay threose, allose, altrose, glucose, seminose, gulose, idose, semi-lactosi or talose,
2. a class according to claim 1 is for the poly-triphenylamine organic hole transport material of the carbohydrate modification of all solid state quantum dot sensitized solar cell, and the value that it is characterized in that the polymerization degree n of described poly-triphenylamine parent is arbitrary numerical value of 20～50.
3. a class according to claim 1 is for the poly-triphenylamine organic hole transport material of the carbohydrate modification of all solid state quantum dot sensitized solar cell, it is characterized in that quantum dot sensitized solar cell is to assemble by following step: at first the organic hole transport material is dissolved in acetonitrile, methylene dichloride, any one solvent of ethanol, is made into the dilute solution that concentration is 0.01～0.5mol/L; Then the method by spin coating drips in the light anode of quantum dot sensitized solar cell, allows solvent evaporates; Finally gold is evaporated on the above-mentioned light anode that contains the organic hole transport material electrode.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4741603A (en) * | 1985-05-08 | 1988-05-03 | Nissan Motor Co., Ltd. | Electrochromic nonglaring mirror |
| EP1261049A1 (en) * | 2001-05-24 | 2002-11-27 | Delphi Technologies, Inc. | Electrode grid for lead acid batteries coated with a conductive polymeric matrix and method of manufacture |
| CN1760235A (en) * | 2005-10-18 | 2006-04-19 | 武汉大学 | Method for synthesizing polymer of poly-triphenylamine |
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| JP2001085272A (en) * | 1999-07-14 | 2001-03-30 | Matsushita Electric Ind Co Ltd | Variable capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4741603A (en) * | 1985-05-08 | 1988-05-03 | Nissan Motor Co., Ltd. | Electrochromic nonglaring mirror |
| EP1261049A1 (en) * | 2001-05-24 | 2002-11-27 | Delphi Technologies, Inc. | Electrode grid for lead acid batteries coated with a conductive polymeric matrix and method of manufacture |
| CN1760235A (en) * | 2005-10-18 | 2006-04-19 | 武汉大学 | Method for synthesizing polymer of poly-triphenylamine |
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| JP特开2001-85272A 2001.03.30 |
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