CN102617832A - 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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- CN102617832A CN102617832A CN201210052245XA CN201210052245A CN102617832A CN 102617832 A CN102617832 A CN 102617832A CN 201210052245X A CN201210052245X A CN 201210052245XA CN 201210052245 A CN201210052245 A CN 201210052245A CN 102617832 A CN102617832 A CN 102617832A
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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 one type of carbohydrate is modified.
[background technology]: the problem that volatilization is revealed, had a strong impact on the stability of battery, be difficult to satisfy 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 has only one kind of spiro-OMeDAT at present; Also be from dye sensitization solar battery, to lend; Be not well positioned to meet the needs of quantum dot sensitized solar cell; So efficient very low (being far smaller than 1%), organic hole transport material ionogen also is not developed out efficiently.
The organic hole transport material that is used for quantum dot sensitized solar cell should have: the hole mobility that (1) is higher; (2) contact between organic hole transport material and the porous titanium dioxide film will be got well; 3) electronics and the dark reaction between the hole in the hole mobile material that are injected in the titanium dioxide film are little.Triphenylamine has higher hole mobility, and with the triphenylamine polymerization, makes poly-triphenylamine as the p-N-type semiconductorN, can make the hole at the intramolecularly fast transferring, further improves the mobility in hole, is very potential one type of organic hole transport material.The electronics and the dark reaction between the hole in the hole mobile material that how to improve the contact of poly-triphenylamine molecule and poriferous titanium dioxide film and suppress in the 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 the sugar, make this sugar-modified poly-triphenylamine to 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 document to having announced are retrieved, and do not find associated viscera.Patent of the present invention has obvious practicability, novelty and novelty.
[summary of the invention]: the present invention makes full use of the characteristic that hydroxyl can adsorb on titanium dioxide film; Utilize saccharide compound that poly-triphenylamine is modified; Thereby obtained the verivate of a series of poly-triphenylamines; And it is used in the quantum dot sensitized solar cell as hole mobile material, obtained good effect.Utilizing the interactional notion 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 verivates that in patent of the present invention, prepare are to be applied in all solid state quantum dot sensitized solar cell as the organic hole transport material for the first time, and the result compares with existing result and also has advance.
[technical scheme of the present invention]:
Exist a large amount of hydroxyls on the surface of titanium dioxide nano material, therefore can form hydrogen bond with the hydroxyl in the sugar; 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 sugared hydroxyl in oxygen combine, form co-ordination bond.This hydrogen bond and co-ordination bond acting in conjunction can make that the contact performance between sugar-modified poly-triphenylamine and the porous titanium dioxide film greatly improves, and help improving the performance of battery.On the other hand, the dark reaction between the electronics of injection titanium oxide and the hole of hole mobile material is carried out through 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 adopted is poly-hydroxy aldehyde; Be to contain great amount of hydroxy group in the molecule; End at molecule has aldehyde radical simultaneously; Utilize the Wittig reaction of the phosphorus ylide reagent (2) of aldehyde radical and poly-triphenylamine base, corresponding carbohydrate is incorporated on the poly-triphenylamine through two keys.Therefore, the synthetic the first step is the phosphorus ylide reagent (2) of preparation poly-triphenylamine base.
Phosphorus ylide reagent (2) the preparation process of poly-triphenylamine base: with substituted poly-triphenylamine of iodomethyl (1) and triphenyl phosphorus reaction; Obtain quaternary alkylphosphonium salt, then quaternary alkylphosphonium salt that obtains and highly basic are reacted the phosphorus ylide reagent (2) that obtains corresponding poly-triphenylamine base under nitrogen protection.With the phosphorus ylide reagent (2) of the poly-triphenylamine base that obtains and any one reaction of Glycerose, erythrose, threose, ribose, pectinose, wood sugar, Lay threose, allose, altrose, glucose, seminose, gulose, idose, semi-lactosi and talose accordingly, just obtained corresponding sugar-modified poly-triphenylamine (3).
The assembling process of described all solid state quantum dot sensitized solar cell is following:
1) adopt the method for silk screen printing that titania slurry is printed on the conductive glass (4); Number of times control thickness through printing; With printed titanium dioxide film high-temperature calcination, removing the organism in the slurry, and improve the contact tightness degree between the titania nanoparticles; 2) titanium dioxide film (5) after the calcining immerses the aqueous solution of halfcystine; Use acetone then; Put into the toluene solution of CdSe quantum dot at last; CdSe quantum dot (6) is adsorbed on obtains light anode, 3 on the titanium dioxide electrodes) synthetic organic hole transport material (7) is dissolved in volatile acetonitrile, methylene dichloride, any one solvent of ethanol, concentration is 0.01～0.5mol/L; 4) method of above-mentioned solution with spin coating dripped on the light anode, so that 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,, obtain complete all solid state quantum dot sensitized solar cell as counter electrode (8).
The all solid state quantum dot sensitized solar cell of said material assembling reached～electricity conversion of 1-2%.
Said one type of poly-triphenylamine organic hole transport material that is used for the carbohydrate modification of all solid state quantum dot sensitized solar cell; It is characterized in that described organic hole transport material is parent with the poly-triphenylamine, introduce saccharide compound in a position of poly-triphenylamine group and modify.
Described one type of poly-triphenylamine organic hole transport material that is used for the carbohydrate modification of all solid state quantum dot sensitized solar cell, the value that it is characterized in that the polymerization degree n of said poly-triphenylamine parent is arbitrary numerical value of 20-50.
Described one type of poly-triphenylamine organic hole transport material that is used for the carbohydrate modification 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.
Described one type of poly-triphenylamine organic hole transport material that is used for 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 through 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; Method through spin coating drips in the light anode of quantum dot sensitized solar cell then, lets solvent evaporates; At last golden counter electrode is evaporated on the above-mentioned light anode that contains the organic hole transport material.
[advantage of the present invention and effect]: patent of the present invention provides one type of poly-triphenylamine organic hole transport material that is used for the carbohydrate modification of all solid state quantum dot sensitized solar cell; It has the following advantages and beneficial effect: 1) triphenylamine has higher hole mobility as the p-N-type semiconductorN, and with the triphenylamine polymerization; Make poly-triphenylamine; Can make the hole at the intramolecularly fast transferring, further improve the mobility in hole, be very potential one type of 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 the sugar; Make this sugar-modified poly-triphenylamine can be adsorbed on the poriferous titanium dioxide film preferably; Increase the contact of itself and poriferous titanium dioxide film, and suppressed dark reaction, obtained good effect.
[description of drawings]:
Fig. 1 is a 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 further specified, 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 THF, then the 1mmol polymerization degree is about 20 the substituted poly-triphenylamine of iodomethyl (1) and drips slowly in above-mentioned solution, stirring at room 24 hours is washed the deposition that obtains drying with ether.Then dried solid is dissolved in the 200mL THF, nitrogen protection adds the NaH of 40mmol down, and stirring at room 20 hours obtains phosphorus ylide (2).5mmol is dissolved in the 20mL THF with phosphorus ylide (2); Any one of the corresponding Glycerose of adding 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 being poured in the water and wash, and extract organic product with anhydrous diethyl ether, the organic phase that obtains use anhydrous sodium sulfate drying, and rotary evaporation is except that desolvating.The solid that obtains separates purification (is eluent with the sherwood oil) 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 THF, then the 1mmol polymerization degree is about 50 the substituted poly-triphenylamine of iodomethyl (1) and drips slowly in above-mentioned solution, stirring at room 24 hours is washed the deposition that obtains drying with ether.Then dried solid is dissolved in the 200mL THF, nitrogen protection adds the NaH of 80mmol down, and stirring at room 20 hours obtains phosphorus ylide (2).1mmol is dissolved in the 20mL THF with phosphorus ylide (2); Any one of the corresponding Glycerose of adding 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 being poured in the water and wash, and extract organic product with anhydrous diethyl ether, the organic phase that obtains use anhydrous sodium sulfate drying, and rotary evaporation is except that desolvating.The solid that obtains separates purification (is eluent with the sherwood oil) 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 THF, is to be about 35 the substituted poly-triphenylamine of iodomethyl (1) to drip slowly in above-mentioned solution with the 1mmol polymerization degree then, and stirring at room 24 hours is washed the deposition that obtains drying with ether.Then dried solid is dissolved in the 200mL THF, nitrogen protection adds the NaH of 70mmol down, and stirring at room 20 hours obtains phosphorus ylide (2).1mmol is dissolved in the 20mL THF with phosphorus ylide (2); Any one of the corresponding Glycerose of adding 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 being poured in the water and wash, and extract organic product with anhydrous diethyl ether, the organic phase that obtains use anhydrous sodium sulfate drying, and rotary evaporation is except that desolvating.The solid that obtains separates purification (is eluent with the sherwood oil) 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 the conductive glass (4), the prescription of titania slurry is: 0.26g TKK 021 and 0.95g titania nanoparticles (P25) are dispersed in the 5mL Terpineol 350.Print 1 layer, obtain the titanium dioxide film of 2 micron thick,, removing the organism in the slurry, and improve the contact tightness degree between the titania nanoparticles 450 ℃ of printed titanium oxide calcining half a hour; 2) titanium dioxide film for preparing (5) immerses the aqueous solution of halfcystine, 70 ℃ of held 1 hour, uses acetone then.Put into the toluene solution of CdSe quantum dot at last, 24 hours, obtain the titanium dioxide electrodes of quantum dot (6) sensitization, i.e. the light anode; 3) with synthetic organic hole transport material (7), the poly-triphenylamine of glucose modified is dissolved in the acetonitrile, and concentration is 0.25mol/L; 4) method of above-mentioned solution with spin coating dripped on the light anode, so that organic hole transport material solution is better immersed in the light anode, and the volatilization of accelerated solvent; 5) treat that solvent evaporates is dried, containing steaming gold on the light anode of organic hole transport material, as counter 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 assembling all solid state quantum dot sensitized solar cell is identical with above-mentioned process, and corresponding efficient sees the following form.
Sugar-modified poly-triphenylamine is assembled into the efficient table of battery
| ? | Efficient |
| 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 (4)
1. one type of poly-triphenylamine organic hole transport material that the carbohydrate that is used for all solid state quantum dot sensitized solar cell is modified; It is characterized in that described organic hole transport material is parent with the poly-triphenylamine, introduce saccharide compound in a position of poly-triphenylamine group and modify.
2. one type of poly-triphenylamine organic hole transport material that is used for the carbohydrate modification of all solid state quantum dot sensitized solar cell according to claim 1, the value that it is characterized in that the polymerization degree n of said poly-triphenylamine parent is arbitrary numerical value of 20-50.
3. one type of poly-triphenylamine organic hole transport material that is used for the carbohydrate modification of all solid state quantum dot sensitized solar cell according to claim 1 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.
4. according to the described one type of poly-triphenylamine organic hole transport material that is used for the carbohydrate modification of all solid state quantum dot sensitized solar cell of claim 1-3; It is characterized in that quantum dot sensitized solar cell is to assemble through 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; Method through spin coating drips in the light anode of quantum dot sensitized solar cell then, lets solvent evaporates; At last golden counter electrode is evaporated on the above-mentioned light anode that contains the organic hole transport material.
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| CN201210052245XA CN102617832B (en) | 2012-03-02 | 2012-03-02 | Poly triphenylamine organic electron hole transmission material for carbohydrate modification of full-solid-state quantum dot sensitized solar cell |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4741603A (en) * | 1985-05-08 | 1988-05-03 | Nissan Motor Co., Ltd. | Electrochromic nonglaring mirror |
| JP2001085272A (en) * | 1999-07-14 | 2001-03-30 | Matsushita Electric Ind Co Ltd | Variable capacitor |
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4741603A (en) * | 1985-05-08 | 1988-05-03 | Nissan Motor Co., Ltd. | Electrochromic nonglaring mirror |
| JP2001085272A (en) * | 1999-07-14 | 2001-03-30 | Matsushita Electric Ind Co Ltd | Variable capacitor |
| 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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