CN104319100B - Double-charge organic hole-transport material for solar cell - Google Patents
Double-charge organic hole-transport material for solar cell Download PDFInfo
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- CN104319100B CN104319100B CN201410645035.0A CN201410645035A CN104319100B CN 104319100 B CN104319100 B CN 104319100B CN 201410645035 A CN201410645035 A CN 201410645035A CN 104319100 B CN104319100 B CN 104319100B
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- transport material
- organic hole
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- quantum dot
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Abstract
The invention discloses double-charge organic hole-transport material for a fully-solid-state quantum dot sensitized solar cell. The double-charge organic hole-transport material is characterized in that m-dinitrobenzene and azoxybenzene serve as two active centers of the organic hole-transport material, when the cell works, two holes can be transported, R1 is any one of hydroxyl and carboxyl, n ranges from 1 to 6, and R2 is a hydrogen atom and can also be alkane with the number of carbon atoms being less than 6.
Description
【Technical field】：The invention belongs to technical field of solar batteries, more particularly, to a class double charge organic hole
Application of the transmission material in all solid state quantum dot sensitized solar cell.
【Background technology】：Quantum dot sensitized solar cell using narrow with gaps inorganic-quantum-dot (quantum dots,
QDs) material such as CdSe, CdS absorption makes on the inorganic semiconductor such as titanium dioxide of with gaps wide as light anode.This
The inorganic-quantum-dot material for planting narrow with gaps has the following advantages that：1) the size realization that the with gaps of QDs can be by changing particle can
Control regulation, and then the spectral response range of QDs can be regulated and controled, to reach the matching good with solar spectrum；2) QDs has high
Molar extinction coefficient, can improve the utilization rate of sunshine；3) quantum dot sensitized solar cell can be produced using thermoelectron
Multiple electron hole pairs, therefore with theoretical conversion efficiency (44%) higher.
Electrolyte usually dissolves oxidation-reduction pair as the important composition material of quantum dot sensitized solar cell
Prepared in specific solvent.In the work of battery, by transmitting the regeneration of electrically realized QDs to QDs, and by time
Pole receives electronics and battery is completed a complete circulation.Therefore, the performance of electrolyte is to quantum dot sensitized solar cell
Efficiency have vital influence.Conventional electrolyte is many sulphur electrolyte with water as solvent at present.However, it is this with
Inevitably there is volatilization leakage in the electrolyte that water makees solvent, had a strong impact on the stability of battery, it is difficult to full
The need for sufficient practical application.Can be assembled into instead of liquid electrolyte using organic hole transport material all solid state quantum dot sensitized
Solar cell, can solve the volatilization leakage problem of liquid electrolyte.The organic hole transport material spiro- for reporting at present
OMeDAT, is also to be lent from DSSC, can not well meet quantum dot sensitization solar electricity
The need for pond, therefore efficiency is very low (far smaller than 1%), and efficient organic hole transport material electrolyte is not developed also
Out.
Organic hole transport material for quantum dot sensitized solar cell should have：(1) hole migration higher
Rate, can effectively realize charge migration, and multiple electron hole pairs are produced in order to match quantum dot sensitized battery thermoelectron, and hole passes
Defeated material is preferably formed with multiple hole transport centers, realizes energy level Optimized Matching；(2) organic hole transport material and porous dioxy
The contact changed between titanium film will get well；3) it is injected into dark between the hole in the electronics and hole mobile material in titanium dioxide film
Reaction is small.
Based on this, this patent proposes that a class is used for the double charge organic hole biography of all solid state quantum dot sensitized solar cell
Defeated material, it is characterised in that described organic hole transport material is using MDNB and azoxybenzene as two work
Property center, when battery operated, can transmit two holes.R1It is hydroxyl or any one of carboxyl, on the one hand increased sky
The contact of hole transport materials and titanium dioxide film, on the other hand, this effect inhibits electronics and hole in titanium dioxide
Hole in transmission material it is compound, reduce dark reaction, achieve good effect.Patent and document to having announced are carried out
Retrieval, does not find related content.Patent of the present invention has obvious practicality, novelty and novelty.
【The content of the invention】：When quantum dot sensitized solar cell working, quantum dot sensitized solar cell can be with
Multiple electron hole pairs are produced using thermoelectron, therefore, organic hole transport material of the design with double charge transfer function, energy
Enough thermoelectrons of matching well produce the feature of multiple electron hole pairs, and this is not carried in conventional research paper and patent
Go out, present invention firstly provides this concept.As realizing carrier, the present invention propose a class for it is all solid state it is quantum dot sensitized too
The double charge organic hole transport material of positive energy battery, it is characterised in that described organic hole transport material is with following
Molecular structure, wherein, MDNB and azoxybenzene are respectively as two activated centres, when battery operated, Ke Yichuan
Defeated two holes, R1It is hydroxyl and any one of carboxyl, n=1~6, R2It is hydrogen atom, or carbon number is less than 6
Alkane.
When battery operated, the hole on quantum dot can pass to two holes of MDNB and azoxybenzene and connect
By unit, different according to hole energy level, typically, high level hole is tended to be combined with MDNB unit, low-lying level hole
Easily combined with azoxybenzene center, this is advantageously implemented the rapidly and efficiently transfer of electric charge, it is also possible to improve open-circuit voltage,
Finally give electricity conversion higher.Meanwhile, R1It is hydroxyl and any one of carboxyl, both groups can be effective
Absorption is conducive to combining closely for hole mobile material and quantum dot on the surface of titanium dioxide.Wherein, n=1~6, R2It is hydrogen
Atom, or alkane of the carbon number less than 6, the alkyl chain of this extension helps to increase the soft of hole mobile material
Property, suppress crystallization.
【Technical scheme】：
The present invention proposes that a class is used for the double charge organic hole transport material of all solid state quantum dot sensitized solar cell,
It is characterized in that described organic hole transport material is using MDNB and azoxybenzene as two activated centres,
When battery operated, two holes, R can be transmitted1It is hydroxyl and any one of carboxyl, n=1~6, R2It is hydrogen atom, also may be used
Think alkane of the carbon number less than 6.
The present invention proposes double charge organic hole transport material, and with dinitro benzene and azoxybenzene respectively as two
Activated centre realizes it is one of new meaning of the invention；Designed using organic molecule and the concept of inorganic semiconductor interaction
The electrolyte of quantum dot sensitized solar cell, and the utilization of creativeness is carried out to carboxyl and hydroxyl, it is of the invention another new
Meaning, the battery for being assembled achieves good transformation efficiency, as a result with certain advance.
The assembling process of described all solid state quantum dot sensitized solar cell is as follows：
1) titania slurry is printed on electro-conductive glass (1) using the method for silk-screen printing, by the number of times for printing
Control thickness, by printed titanium dioxide film high-temperature calcination, to remove the organic matter in slurry, and improves nano titania
Contact tightness degree between grain；2) titanium dioxide film (2) after calcining immerses the aqueous solution of cysteine, then clear with acetone
Wash, be finally putting into the toluene solution of CdSe quantum dot, adsorb CdSe quantum dot (3) and light sun is obtained on titanium dioxide electrodes
Pole, 3) double charge organic hole transport material (4) is dissolved in volatile acetonitrile, dichloromethane, ethanol any one solvent
In, concentration is 0.01~0.5mol/L；4) method of above-mentioned solution spin coating is added dropwise in light anode, to make organic sky
Hole transport materials solution is preferably immersed in light anode, and accelerates the volatilization of solvent；5) organic hole transport material is being contained
Gold is steamed in light anode, as to electrode (5), complete all solid state quantum dot sensitized solar cell is obtained.
The all solid state quantum dot sensitized solar cell of the material assembling has reached 4% electricity conversion.
【Advantages of the present invention and effect】：Patent of the present invention provides a class is used for all solid state quantum dot sensitized solar cell
Double charge organic hole transport material, it has advantages below and beneficial effect：1) double charge center is contained：MDNB
And azoxybenzene.Different according to hole energy level, high level hole is tended to be combined with MDNB unit, low-lying level hole
Easily combined with azoxybenzene center, this is advantageously implemented the rapidly and efficiently transfer of electric charge, it is also possible to improve open-circuit voltage,
Finally give electricity conversion higher.2) hydroxyl or carboxyl are introduced on double charge organic hole transport material, is utilized
Hydroxyl or carboxyl and titanium dioxide film are acted on, and on the one hand increased the contact of hole mobile material and titanium dioxide film,
On the other hand, this effect inhibits the compound of the hole in electronics and hole mobile material in titanium dioxide, reduces dark
Reaction, achieves good effect.3) cyano group has guide effect as strong electron-withdrawing group group to the displacement of electric charge, carries
Charge mobility high.
【Brief description of the drawings】
Fig. 1 is the structural representation of all solid state quantum dot sensitized solar cell based on double charge organic hole transport material
Figure.
【Specific embodiment】
Present invention is described further with reference to embodiment, but the scope of the present invention is not limited only to following reality
Example is applied, it is every to belong to the equivalent technical scheme of present invention, belong to the protection domain of this patent.
1) titania slurry is printed on electro-conductive glass (1) using the method for silk-screen printing, titania slurry
It is formulated and is：0.26g ethyl celluloses and 0.95g titania nanoparticles (P25) are dispersed in 5mL terpinols.1 layer of printing,
2 microns of titanium dioxide films of thickness are obtained, by printed 450 DEG C of calcining half an hour of titanium dioxide, to remove the organic matter in slurry,
And improve the contact tightness degree between titania nanoparticles；2) titanium dioxide film (2) the immersion cysteine for preparing
The aqueous solution, at 70 DEG C place 1 hour, then cleaned with acetone.The toluene solution of CdSe quantum dot is finally putting into, 24 is small
When, obtain the titanium dioxide electrodes of quantum dot (3) sensitization, i.e. light anode；3) it is molten by double charge organic hole transport material (4)
In acetonitrile, concentration is 0.25mol/L to solution；4) method of above-mentioned solution spin coating is added dropwise in light anode, to make have
Machine hole mobile material solution is preferably immersed in light anode, and accelerates the volatilization of solvent；5) treat that solvent volatilization is dry, containing having
Gold is steamed in the light anode of machine hole mobile material, used as to electrode (5), the thickness of gold is 100nm, obtains complete all solid state amount
Son point sensitization solar battery.The electricity conversion of battery is 4%.
Claims (1)
1. a class is used for the double charge organic hole transport material of all solid state quantum dot sensitized solar cell, it is characterised in that institute
The organic hole transport material stated using MDNB and azoxybenzene as two activated centres, battery operated
When, two holes, R can be transmitted1It is hydroxyl and any one of carboxyl, n=1~6, R2It is hydrogen atom, or carbon atom
Alkane of the number less than 6
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410645035.0A CN104319100B (en) | 2014-11-07 | 2014-11-07 | Double-charge organic hole-transport material for solar cell |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410645035.0A CN104319100B (en) | 2014-11-07 | 2014-11-07 | Double-charge organic hole-transport material for solar cell |
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| CN104319100A CN104319100A (en) | 2015-01-28 |
| CN104319100B true CN104319100B (en) | 2017-05-24 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101694813A (en) * | 2009-09-30 | 2010-04-14 | 中国科学院等离子体物理研究所 | Liquid crystal electrolyte solution for dye-sensitized nano film solar battery |
| CN102603542A (en) * | 2012-03-02 | 2012-07-25 | 河北联合大学 | Saccharide-modified triphenylamine organic hole transport material for all-solid-state quantum dot dye-sensitized solar cell |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4644818B2 (en) * | 2006-09-05 | 2011-03-09 | 国立大学法人群馬大学 | Dye for dye-sensitized solar cell, photoelectric conversion element using the dye, and dye-sensitized solar cell |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101694813A (en) * | 2009-09-30 | 2010-04-14 | 中国科学院等离子体物理研究所 | Liquid crystal electrolyte solution for dye-sensitized nano film solar battery |
| CN102603542A (en) * | 2012-03-02 | 2012-07-25 | 河北联合大学 | Saccharide-modified triphenylamine organic hole transport material for all-solid-state quantum dot dye-sensitized solar cell |
Non-Patent Citations (3)
| Title |
|---|
| A novel alkoxysilyl azobenzene dye photosensitizer with alkylamino group for dye sensitized solar cells;Kenji Kakiage,Yohei Aoyama,et al;《ORIGINAL PAPER》;20140110(第6期);全文 * |
| 偶氮共轭聚合物光电特性研究进展;刘剑，田晶晶，et al;《高分子通报》;20120630(第6期);全文 * |
| 取向碳纳米管/高分子新型复合材料的制备及应用;丘龙斌，孙雪梅，et al;《化学学报》;20120417(第70期);全文 * |
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Inventor after: Li Chunsheng Inventor after: Wang Tong Inventor after: Feng Jia Inventor after: Mao Xiaoliang Inventor after: Sun Yan Inventor after: Liu Haitao Inventor after: Zhang Yu Inventor after: You Zhiguo Inventor after: Shi Jifu Inventor after: Chou Shulei Inventor after: Li Chunying Inventor after: Ma Xuegang Inventor before: Li Chunsheng Inventor before: Zhang Xueya Inventor before: Sun Yan Inventor before: Shi Jifu Inventor before: Ma Xuegang Inventor before: Wang Hong Inventor before: Hu Yiwen Inventor before: Mao Xiaoliang Inventor before: Li Jing Inventor before: Wang Tong |
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Address after: 063009 Hebei province Tangshan City Xinhua West Road No. 46 Patentee after: North China Polytechnics Address before: 063009 Hebei province Tangshan City Xinhua West Road No. 46 Patentee before: Hebei United University |
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Granted publication date: 20170524 Termination date: 20181107 |