CN102604049B - Amino acid modified poly(triphenylamine) organic hole transport material used for all-solid-state quantum dot-sensitized solar cells - Google Patents
Amino acid modified poly(triphenylamine) organic hole transport material used for all-solid-state quantum dot-sensitized solar cells Download PDFInfo
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- CN102604049B CN102604049B CN2012100522337A CN201210052233A CN102604049B CN 102604049 B CN102604049 B CN 102604049B CN 2012100522337 A CN2012100522337 A CN 2012100522337A CN 201210052233 A CN201210052233 A CN 201210052233A CN 102604049 B CN102604049 B CN 102604049B
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Abstract
The invention discloses an amino acid modified poly(triphenylamine) organic hole transport material used for all-solid-state quantum dot-sensitized solar cells. The material is characterized by taking poly(triphenylamine) as a matrix, wherein amino acid molecules are introduced to the site a of poly(triphenylamine) to modify poly(triphenylamine); and the amino acid can be any one of 22 types of the following common amino acids: glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, cystine, methionine, aspartic acid, glutamic acid, asparagine, glutamine, lysine, histidine, arginine, phenylalanine, tyrosine, tryptophan, proline and hydroxyproline.
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 class of amino acid is modified.
[background technology]: vital impact can be arranged the efficiency of quantum dot sensitized solar cell.The best ionogen of result of use is the many sulphur ionogen take water as solvent at present.Yet the problem that this ionogen of making solvent with water inevitably can exist volatilization to reveal, had a strong impact on the stability of battery, is 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 one kind of spiro-OMeDAT at present, also to lend from dye sensitization solar battery, 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.
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 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, with the triphenylamine polymerization, make poly-triphenylamine, can make hole fast transferring in molecule, further improve the mobility in hole, so poly-triphenylamine is a very potential class organic hole transport material.How improving the contact between the titanium dioxide film of poly-triphenylamine organic hole transport material and porous and reducing dark reaction is the current problem of needing solution badly.
Based on this, this patent has been introduced amino acid on the poly-triphenylamine parent, utilize the carboxyl of amino acid molecular to modify poly-triphenylamine, utilize amino and titanium dioxide film effect in amino acid molecular, increased on the one hand the contact of hole mobile material and titanium dioxide film, on the other hand, this effect has suppressed the compound of electronics in titanium dioxide and the hole in hole mobile material, reduce 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 in amino acid molecular and not only contains carboxyl but also contain amino characteristics, utilizes the carboxyl of amino acid molecular to modify poly-triphenylamine, first at a position of poly-triphenylamine introducing-CH
2The OH group, then utilize in amino acid carboxyl and-CH
2The esterification of OH group, introduce amino acid molecular on the poly-triphenylamine parent.
Utilize simultaneously amino and titanium dioxide film effect in amino acid molecular, increase contact and reduce dark reaction.Exist the undersaturated titanium atom of a large amount of coordinations (being called surface state) on the surface of titanium dioxide nano material, the undersaturated titanium atom of these coordinations can trapped electron, then with these electric transmission to hole mobile material, make electronics by compound, dark reaction has also namely occurred, the efficiency that affects battery that the existence meeting of this dark reaction is serious.The present invention utilizes amino and the undersaturated titanium atom of coordination in amino acid to carry out coordination, can reduce the number of this surface state, suppress greatly dark reaction, this coordination can increase the contact of hole mobile material and poriferous titanium dioxide film simultaneously.This all is conducive to the raising of battery performance.
[technical scheme of the present invention]:
The present invention utilizes amino acid molecular to modify poly-triphenylamine, and these hole mobile materials are applied in quantum dot sensitized solar cell for the first time is one of new meaning of the present invention; Utilizing the interactional concept of organic molecule and inorganic semiconductor to design the ionogen of quantum dot sensitization solar battery, and amino acid molecular functional group is comprised that carboxyl and amino carry out creationary utilization, is another new meaning of the present invention.The battery of assembling has been obtained good transformation efficiency, and result has certain advance.
A described class is as follows for the synthetic schemes of the amino acid modified poly-triphenylamine organic hole transport material of all solid state quantum dot sensitized solar cell:
The a bit strip is had-CH
2The poly-triphenylamine of OH group (1) adds SOCl slowly under cryosel bath condition
2In, be stirred to dissolving.Slowly add finally amino acid (any one of glycine, L-Ala, α-amino-isovaleric acid, leucine, Isoleucine, Serine, Threonine, halfcystine, Gelucystine, methionine(Met), aspartic acid, L-glutamic acid, l-asparagine, glutamine, Methionin, Histidine, arginine, phenylalanine, tyrosine, tryptophane, proline(Pro), oxyproline, the mol ratio of amino acid and (1) equals the polymerization degree), reflux.Then excessive SOCl
2Method by rotary evaporation steams.The dissolution of solid that obtains in tetrahydrofuran (THF), passes into ammonia, makes the proton of amino upper combination in product be neutralized, and then is rotated evaporation, and solvent is evaporated, and the solid that obtains carries out purifying by silicagel column, and eluent is petrol ether/ethyl acetate.This reaction is to pass through SOCl
2Reaction first obtains corresponding acyl chlorides with amino acid, and then acyl chlorides and a bit strip have-CH
2The poly-triphenylamine of OH group (1) carries out esterification and obtains amino acid modified poly-triphenylamine organic hole transport material (2).
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 (3), number of times by printing is controlled thickness, with printed titanium dioxide film high-temperature calcination, to remove the organism in slurry, and the contact tightness degree between the raising titania nanoparticles; 2) titanium dioxide film (4) after the calcining immerses the aqueous solution of halfcystine, then clean with acetone, put into finally the toluene solution of CdSe quantum dot, CdSe quantum dot (5) is adsorbed on titanium dioxide electrodes obtains the light anode, the organic hole transport material (6) 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 (7), 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%.
A described class is used for the amino acid modified poly-triphenylamine organic hole transport material of all solid state quantum dot sensitized solar cell, it is characterized in that described organic hole transport material take poly-triphenylamine as parent, introduce amino acid molecular in a position of poly-triphenylamine poly-triphenylamine is modified.
A described class is used for the amino acid modified poly-triphenylamine organic hole transport material of all solid state quantum dot sensitized solar cell, it is characterized in that described amino acid can be common amino acid in 22: any one of glycine, L-Ala, α-amino-isovaleric acid, leucine, Isoleucine, Serine, Threonine, halfcystine, Gelucystine, methionine(Met), aspartic acid, L-glutamic acid, l-asparagine, glutamine, Methionin, Histidine, arginine, phenylalanine, tyrosine, tryptophane, proline(Pro), oxyproline.
A described class is used for the amino acid modified poly-triphenylamine organic hole transport material 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.
A described class is used for the amino acid modified poly-triphenylamine organic hole transport material 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 with gold evaporation 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 a class to be used for the amino acid modified poly-triphenylamine organic hole transport material of all solid state quantum dot sensitized solar cell, it has the following advantages and beneficial effect: 1) on the surface of titanium dioxide nano material, exist the undersaturated titanium atom of a large amount of coordinations, the undersaturated titanium atom of these coordinations can trapped electron, then with these electric transmission to hole mobile material, make electronics by compound, dark reaction has also namely occurred, the efficiency that affects battery that the existence meeting of this dark reaction is serious.2) the present invention utilizes amino and the undersaturated titanium atom of coordination in amino acid to carry out coordination, can reduce the number of this surface state, suppress greatly dark reaction, this coordination can increase the contact of hole mobile material and poriferous titanium dioxide film simultaneously; This all is conducive to the raising of battery performance.
[technical scheme of the present invention]:
The present invention utilizes amino acid molecular to modify poly-triphenylamine, and these hole mobile materials are applied in quantum dot sensitized solar cell for the first time is one of new meaning of the present invention; Utilizing the interactional concept of organic molecule and inorganic semiconductor to design the ionogen of quantum dot sensitization solar battery, and amino acid molecular functional group is comprised that carboxyl and amino carry out creationary utilization, is another new meaning of the present invention.The battery of assembling has been obtained good transformation efficiency, and result has certain advance.
[description of drawings]:
Fig. 1 is the building-up process of organic hole transport material.
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.
0.001mol a bit strip is had-CH
2The polymerization degree of OH group is about 20 poly-triphenylamine (1) (10 ℃) under cryosel bath condition and slowly adds 200mL SOCl
2In, be stirred to dissolving.Then stirring at normal temperature is 10 hours, slowly add finally 0.02mol amino acid (any one of glycine, L-Ala, α-amino-isovaleric acid, leucine, Isoleucine, Serine, Threonine, halfcystine, Gelucystine, methionine(Met), aspartic acid, L-glutamic acid, l-asparagine, glutamine, Methionin, Histidine, arginine, phenylalanine, tyrosine, tryptophane, proline(Pro), oxyproline), refluxed 10 hours, excessive SOCl
2Method by rotary evaporation steams.The dissolution of solid that obtains is in the 100mL tetrahydrofuran (THF), pass into ammonia (2 hours), make the proton of amino upper combination in product be neutralized, then be rotated evaporation, solvent is evaporated, the solid that obtains carries out purifying by silicagel column, and eluent is petrol ether/ethyl acetate (volume ratio is 2/3).
The preparation process of the poly-triphenylamine organic hole transport material of other polymerization degree is identical with above-mentioned preparation process, is the mol ratio of conditioned reaction thing, that is, the mol ratio of amino acid and poly-triphenylamine equals the polymerization degree.
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 conductive glass (3), 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 half an hour, to remove the organism in slurry, and the contact tightness degree between the raising titania nanoparticles; 2) titanium dioxide film for preparing (4) immerses the aqueous solution of halfcystine, places 1 hour under 70 ℃, then with acetone, cleans.Put into finally the toluene solution of CdSe quantum dot, 24 hours, obtain the titanium dioxide electrodes of quantum dot (5) sensitization, i.e. the light anode; The organic hole transport material (6) that 3) will synthesize, the monobasic poly-triphenylamine of glycine, 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 (7), the thickness of gold is 100nm, obtains complete all solid state quantum dot sensitized solar cell.The electricity conversion of battery is 1.9%.
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 is listed in the table below.
Amino acid modified poly-triphenylamine is assembled into the efficiency table of battery
| Efficiency | |
| Glycine | 1.9％ |
| L-Ala | 1.1％ |
| α-amino-isovaleric acid | 1.8％ |
| Leucine | 1.8％ |
| Isoleucine | 1.4％ |
| Serine | 1.9％ |
| Threonine | 1.8％ |
| Halfcystine | 1.8％ |
| Gelucystine | 1.9％ |
| Methionine(Met) | 1.9％ |
| Aspartic acid | 1.1％ |
| L-glutamic acid | 1.8％ |
| L-asparagine | 1.2％ |
| Glutamine | 1.0％ |
| Methionin | 1.1％ |
| Histidine | 1.8％ |
| Arginine | 1.1％ |
| Phenylalanine | 1.7％ |
| Tyrosine | 1.2％ |
| Tryptophane | 1.0％ |
| Proline(Pro) | 1.9％ |
| Oxyproline | 1.7％ |
Claims (3)
1. a class is used for the amino acid modified poly-triphenylamine organic hole transport material 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, introduce the carboxyl of amino acid molecular in a position of poly-triphenylamine poly-triphenylamine is modified, this reaction is to pass through SOCl
2Reaction first obtains corresponding acyl chlorides with amino acid, and then acyl chlorides and a bit strip have-CH
2The poly-triphenylamine of OH group carries out esterification and obtains amino acid modified poly-triphenylamine organic hole transport material; Described amino acid is any one of glycine, L-Ala, α-amino-isovaleric acid, leucine, Isoleucine, Serine, Threonine, halfcystine, Gelucystine, methionine(Met), aspartic acid, L-glutamic acid, l-asparagine, glutamine, Methionin, Histidine, arginine, phenylalanine, tyrosine, tryptophane, proline(Pro), oxyproline;
2. a class according to claim 1 is used for the amino acid modified poly-triphenylamine organic hole transport material 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 used for the amino acid modified poly-triphenylamine organic hole transport material 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 with gold evaporation on the above-mentioned light anode that contains the organic hole transport material.
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| CN109244243A (en) * | 2018-09-06 | 2019-01-18 | 中国石油大学(华东) | A kind of L-cysteine modification TiO2The methods and applications of electron transfer layer |
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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 |
| CN1760235A (en) * | 2005-10-18 | 2006-04-19 | 武汉大学 | Method for synthesizing polymer of poly-triphenylamine |
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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 |
| CN1760235A (en) * | 2005-10-18 | 2006-04-19 | 武汉大学 | Method for synthesizing polymer of poly-triphenylamine |
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