CN103665047A - Application of novel ligand compound in dye-sensitized solar cell - Google Patents
Application of novel ligand compound in dye-sensitized solar cell Download PDFInfo
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- CN103665047A CN103665047A CN201210363431.5A CN201210363431A CN103665047A CN 103665047 A CN103665047 A CN 103665047A CN 201210363431 A CN201210363431 A CN 201210363431A CN 103665047 A CN103665047 A CN 103665047A
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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
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- Y02E10/542—Dye sensitized solar cells
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Abstract
The invention designs and prepares a novel dye-sensitized metal ligand compound applied to a dye-sensitized solar cell through effective molecular engineering, so that the molar absorption coefficient of a solar radiation red spectral region can be improved, and the efficiency of injecting electrons in a dye-excited state into a titanium dioxide semiconductor is effectively improved. Thus, the dye-sensitized solar cell with higher efficiency and longer service life is developed. The invention also relates to a method for fabricating the dye-sensitized solar cell by using the metal ligand compound.
Description
Technical field
The present invention relates to be applied to the Design & preparation of " antenna " metal ligand compound in dye sensitization solar battery (sensitization solar battery), and the making method of the solar cell that contains same metal ligand compound.
Background technology
Dye sensitization solar battery, is a renewable energy resources battery based on photoelectrochemistry principle, and its primary member comprises: a light anode, a counter electrode, and the electrolytic solution between these two electrodes.The groundwork chemical composition of dye sensitization solar battery is photosensitive dye, electrolytic solution (for example, iodide ion/Iodine molecule ion), and the semiconductor material based on nano-form (for example, titanium dioxide).
The height of the photoelectric transformation efficiency of solar cell is the quantity depending on the photon of whole solar radiation spectrum results, and the quantity that is injected into semi-conductive quick electronics.As shown in Figure 1, when light source impinges upon on battery, the electronics in photosensitizers is from ground state transition to excited state, and the conduction band that is then injected into titanium dioxide gets on.
It is upper that light-sensitive coloring agent is adsorbed on light anode (for example, nano titanium oxide), and contact with electrolytic solution.Yet, be not the electronics of all injection nano titanium oxide conduction bands can be transferred to external circuit on electrode, this is because of the interface between electron injection and sensitized material oxidation state and on the interface between electron injection and electrolytic solution, the possibility that exists charge recombination to bury in oblivion.Therefore, molecular engineering can be used for designing the photosensitive material of novel sun power, make its absorption spectrum covering visible light and near infrared region widely, collect maximum photons and convert electronics to, again effectively by electronic injection to conduction band, and minimum, the such composite design that may drop to that charge recombination is buried in oblivion will be ideal state.
Light-sensitive coloring agent can be metal-free organic dye or the complex dye that contains metal.Than metal-free organic dye, in general complexed metal dyestuff shows and is showing better photostabilization and solar energy photoelectric conversion efficiency.Ruthenium basigamy metal dyestuff, is better than other transition metal and comprises copper, iron etc.They consist of ruthenium and one " anchor " conventionally, can be the title complexs or do not have with " antenna " part.On the one hand, the effect of " anchor " is to guarantee that chromophoric group is anchored on anode, and on the other hand, " antenna " part contributes to expand to catch the spectral range of solar radiation light, and is showing raising molar absorptivity, thereby more efficiently transform light energy is become to electric energy.
At present, the subject matter of dye sensitization solar battery, comprise that cannot cover complete solar radiation spectrum (contains height, low-energy photon), particularly cannot cover red spectral region, and the electronic injection titanium dioxide semiconductor inefficiency of dyestuff excited state, lower molar absorptivity etc.By effective molecular engineering, the molecular structure of design dye sensitization " antenna " can effectively address the above problem.Therefore, " antenna " part of new generation, for the more efficient and sane dye sensitization solar battery of development, is urgently necessary.
Summary of the invention
On the one hand, the present invention has designed " antenna " part using at dye sensitization solar battery." antenna " part has following structure:
" antenna " ligand molecular-1
On the other hand, the metallo-chelate that further invention is above-mentioned by containing " antenna " ligand structure is applied to dye sensitization solar battery, and details is described below.
The present invention will explain in detail at following drawing, and cited patent documentation discloses in reference.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of semi-conductive each integral part of dye sensitized nano crystal salar battery.
Fig. 2 is the quantum yield comparison that photon conversion becomes electronics, sensitizing dye molecule-1, sensitizing dye molecule-2 and canonical reference dyestuff.
Embodiment
" antenna " group and antenna ligand molecule
As mentioned above, first aspect of the present invention is one and uses " antenna " part at dye sensitization solar battery." antenna " ligand molecular has following structure:
" antenna " ligand molecular-1
Except said structure, in some embodiments, " antenna " ligand groups contains other derived structures,
As following structure:
" antenna " ligand molecular-2
" antenna " ligand molecular-3
Anchoring group and metal complexes
In dye sensitization solar battery, normally with one metal of " antenna " of the present invention part and at least one anchoring group compound use.In the ordinary course of things, this mixture comprises:
(1) metal, as, osmium, iridium, rhenium, rhodium, iron and ruthenium;
(2) one to two organic anchoring groups, for example, (one, two, three or four) heterocycle metal-chelating group, comprising, but be not limited only to carboxyl (COOH), phosphate (PO
3h
2,-PO
4h
2), sulfonic group (SO
3h
2,-SO
4h
2), amide group (CONHOH), and the derivative form of their its deprotonations.
(3) one to two organic " antenna " parts, as mentioned above;
(4) zero to two other groups, for example, and hydroxyl (OH), halogen group (X), cyano group (CN), isocyano-(NCO ,-NCS, and NCSe)
The example of metal complexes of the present invention comprises, but is not only confined to as follows:
Sensitizing dye metal complexes-1
Sensitizing dye metal complexes-2
Dye sensitization solar battery
The present invention, the preparation of " antenna " mentioned above by containing group metal complexes, in conjunction with using known dye sensitization solar battery technology, for example, United States Patent (USP) (patent No. 5350644,6479745,7145071,7157788,7332782,7989691,7932404), realize the dye sensitization solar battery of Optimal performance more, be specifically implemented as follows:
The invention provides a reproducible photoelectrochemical cell, comprising: light anode (be at least one semiconductor alloy lead oxide layer materials as cell substrates), light-sensitive coloring agent, one to electrode, and at light anode with to the ionogen between electrode, light-sensitive coloring agent is wherein a metal ligand compound that contains as mentioned above " antenna " group.
In certain embodiments, amphipathic molecular structure comprises at least one anchoring group, a hydrophobic part and a terminal group, and light-sensitive coloring agent monolayer adsorption is on semiconduction metal oxide layer.
In certain embodiments, hydrophilic radical is selected from alkyl carboxylic acid, alkyl dicarboxylic aid, alkyl carboxylic acid, alkyl phosphonic acid, phosphonate ester, alkyl phosphonic acid Alkyl diphosphonate salt, alkylsulphonic acid amino acid, alkylsulfonate, alkyl hydroximic acid, wherein said alkyl can be linear, or dendroid, contain one to 12 carbon atom.Its hydrophobic chain part can be given prominence on light-sensitive coloring agent monomolecular layer.
In certain embodiments, ionogen is a redox system, comprises the salt of electrochemical activity and forms salt anionic or a cationic, oxidized reduction group of appealing said electrochemical activity.In electrolytic solution, also comprise polar organic solvent, its boiling point is depressed at normal atmospheric, be equal to or greater than 100 Celsius, butyronitrile for example.
embodiment
The following examples and effect data are beneficial effects that how to implement and of the present invention in order to illustrate the present invention, but protection scope of the present invention is not limited to these specific embodiments.Contriver endeavours to ensure the accuracy of example, as quantity, temperature etc., but does not get rid of some mistakes and deviation.Except as otherwise noted, composition is by weight, and temperature is degree Celsius that pressure approaches barometric point.
Plant and instrument
NMR (Nuclear Magnetic Resonance) spectrum is provided by Brooker 400 nuclear magnetic resonance spectrometers, infrared spectra is provided by Shimadzu infrared spectrophotometer spectrum, absorption spectrum is recorded on ultraviolet/Vis/NIR instrument of Perkin Elmer company, fluorescence spectrum is recorded in the fluorescence spectrophotometer of Yi Ge Jobin-Yvon company, all microscopic patterns are observed and are completed by scanning electronic microscope, and the PW3020 of X ray film diffraction PHILIPS Co. is upper definite.
Synthesizing of " antenna " group part
The synthetic of " antenna " group part is to carry out in a penstock.By 4,4 '-dimethyl-2, (2 grams of 2 '-dipyridyls, 0.0108 mole), 4-N, and N-diphenyl amino-1-formaldehyde (5.92 grams, 0.0217mol), (7.02 grams of trimethylchlorosilanes, 0.065mol), and 70 milliliters of anhydrous dimethyl formamides (DMF) solvent pour penstock into, magnetic agitation, temperature of reaction is brought up to 100 degrees Celsius, and continuously stirring is reacted 2 days.In reaction process, the color of reaction mixture becomes yellow, becomes orange after cooling and relief pressure.Rotary evaporation, except desolventizing, adds water washing, and filters under vacuum, obtains orange " antenna " group part, 85% productive rate.Molecular formula is shown " antenna " group part synthetic route.
The synthetic route of " antenna " group ligand molecular-1
Synthesizing of sensitizing dye metal complexes-1
Be shown below, sensitizing dye metal complexes synthetic can carry out three-step reaction and complete in a reactor.Reactor is the reaction flask of 250 milliliters; condenser and magnetic agitation be equipped with; under nitrogen protection; in flask, add 100 milliliters of anhydrous dimethyl formamides (DMF); two chloro-ruthenium (II) dipolymers (0.2 gram) and above-mentioned " antenna " group ligand compound (0.453 gram, 0.00065 mole).Reaction mixture is stirred 3 hours under 90 degree, then, by 2,2 '-dipyridyl-4,4 '-dicarboxylic acid (0.159 gram, 0.00065mol) add, and temperature is elevated to 130 degree, stir after 16 hours, by NH
4nCS joins in reaction mixture, at 130 degree, continues reaction 8 hours.After having reacted, be cooled to room temperature, rotary evaporation is removed solvent DMF, adds ionized water and ether washing, and filters under vacuum, and desciccate spends the night, 78% productive rate.
The synthetic route of sensitizing dye metal complexes-1
Solar cell properties
Under identical condition, contrast standard dyestuff (two-tetrabutylammonium cis-bis-(isothiocyano) two (2,2 '-dipyridyl-4,4 '-dicarboxyl) ruthenium (II) (the product #703214 of Sigma aldrich company), the performance of having tested respectively above-mentioned novel sensitizing dye metal complexes 1 and 2.The lighting condition of standard: AM1.5 (100 milliwatt/square centimeter).Photon-electronic switch quantum yield (IPCE) performance as shown in Figure 2, short-circuit photocurrent density (Jsc), open circuit photovoltage voltage (Voc), packing factor (FF), and total sun power-electricity is changed as shown in table 1.
| Table 1: sunlight-electric energy conversion | ||||
| Dyestuff | Battery performance parameter | |||
| Jsc(mA/cm 2) | Voc(V) | FF | Efficiency(％) | |
| #703214 (canonical reference) | 17.1 | 0.72 | 0.73 | 9.2 |
| DSSC Dye#1 (sensitizing dye-1) | 20.6 | 0.71 | 0.71 | 10.4 |
| DSSC Dye#2 (sensitizing dye-2) | 19.9 | 0.66 | 0.71 | 9.3 |
In present specification, in conjunction with specific embodiments, the present invention is described in detail, but to those skilled in the art, obviously can to it, makes various changes and modifications without departing from the case in the spirit of the invention.All this type of changes and modification should be thought within the scope of claims of all falling into the application.
Claims (10)
1. for the metal ligand compound that contains " antenna " group of sensitizing dye solar cell.
2. the metal ligand compound that contains " antenna " group described in claim 1, the metal-chelating group of the fragrant heterocycle that comprises one or more bidentates or three teeth, has at least one " antenna " group.
3. the ligand compound that contains " antenna " group described in claim 1 to 2 has following structural formula:
R wherein
1and R
2represent independently of one another " antenna " group.
4. " antenna " described in claims 1 to 3 group has following structural formula:
5. a metal-organic complex can be used as dyestuff, is applied in sensitizing dye solar cell, and metal complexes wherein comprises:
(1) metal, is selected from ruthenium, osmium, iridium, rhenium, rhodium, and the metallic element such as iron;
(2) one to two bidentates or three teeth are for the organic ligand of " grappling ";
(3) one to two bidentates or the ligand that three teeth are organic contains " antenna " group;
(4) zero to two monodentate ligands, comprising: carboxyl, hydrogen-oxygen group, halogeno-group, cyano group, isocyanato (NCO), isocyanide sulfate (NCS) etc.;
Improvements of the present invention comprise: adopting at least one is according to the ligand of " antenna " described in claim 1 to 4.
6. the organic ligand for " grappling " described in claim 5, be (one, two, three or four) heterocycle metal-chelating group, comprising, but be not limited only to carboxyl (COOH), phosphate (PO3H2,-PO4H2), sulfonic group (SO3H2 ,-SO4H2), amide group (CONHOH), and the derivative form of their its deprotonations.
7. a metal-organic complex that can be used as dyestuff described in claim 5 can be following structure:
Sensitizing dye metal complexes-1
With following structure:
Sensitizing dye metal complexes-2
8. a reproducible photoelectrochemical cell, comprising: light anode (be at least one semiconductor alloy lead oxide layer materials as cell substrates), light-sensitive coloring agent, one to electrode, and at light anode with to the ionogen between electrode, light-sensitive coloring agent is wherein a metal ligand compound for claim 5 to 7 " antenna " group as mentioned above.
9. the reproducible photoelectrochemical cell described in claim 8, wherein said light-sensitive coloring agent is an amphipathic molecular structure, comprise at least one anchoring group, a hydrophobic part and a terminal group, monolayer adsorption is on semiconduction metal oxide layer.Its hydrophilic radical is selected from alkyl carboxylic acid, alkyl dicarboxylic aid, alkyl carboxylic acid, alkyl phosphonic acid, phosphonate ester, alkyl phosphonic acid Alkyl diphosphonate salt, alkylsulphonic acid amino acid, alkylsulfonate, alkyl hydroximic acid, wherein said alkyl can be linear, or dendroid, contains one to 12 carbon atom.Its hydrophobic chain part can be given prominence on light-sensitive coloring agent monomolecular layer.
10. the reproducible photoelectrochemical cell described in claim 8, wherein said ionogen is a redox system, comprises the salt of electrochemical activity and forms salt anionic or the cationic, oxidized reduction group of a said electrochemical activity of appeal.In electrolytic solution, also comprise polar organic solvent, its boiling point is depressed at normal atmospheric, be equal to or greater than 100 Celsius, comprising, but be not limited only to butyronitrile.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105006523A (en) * | 2015-08-26 | 2015-10-28 | 电子科技大学 | Iridium complex doped triplet solar cell |
| CN105070837A (en) * | 2015-08-26 | 2015-11-18 | 电子科技大学 | Iridium-complex-doped three-element solar cell |
| WO2017047410A1 (en) * | 2015-09-17 | 2017-03-23 | 富士フイルム株式会社 | Photoelectric conversion element, dye-sensitized solar cell, dye composition, and oxide semiconductor electrode |
| CN106801231A (en) * | 2017-02-07 | 2017-06-06 | 辽宁大学 | The WO of molecular level iridium catalyst modification3Complex light anode and its application |
| EP3584814A4 (en) * | 2017-02-17 | 2020-12-16 | Fujifilm Corporation | Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye composition, and oxide semiconductor electrode |
-
2012
- 2012-09-26 CN CN201210363431.5A patent/CN103665047A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105006523A (en) * | 2015-08-26 | 2015-10-28 | 电子科技大学 | Iridium complex doped triplet solar cell |
| CN105070837A (en) * | 2015-08-26 | 2015-11-18 | 电子科技大学 | Iridium-complex-doped three-element solar cell |
| WO2017047410A1 (en) * | 2015-09-17 | 2017-03-23 | 富士フイルム株式会社 | Photoelectric conversion element, dye-sensitized solar cell, dye composition, and oxide semiconductor electrode |
| JPWO2017047410A1 (en) * | 2015-09-17 | 2018-02-01 | 富士フイルム株式会社 | Photoelectric conversion element, dye-sensitized solar cell, dye composition and oxide semiconductor electrode |
| CN106801231A (en) * | 2017-02-07 | 2017-06-06 | 辽宁大学 | The WO of molecular level iridium catalyst modification3Complex light anode and its application |
| CN106801231B (en) * | 2017-02-07 | 2019-01-01 | 辽宁大学 | The WO of molecular level iridium catalyst modification3Complex light anode and its application |
| EP3584814A4 (en) * | 2017-02-17 | 2020-12-16 | Fujifilm Corporation | Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye composition, and oxide semiconductor electrode |
| US11094474B2 (en) | 2017-02-17 | 2021-08-17 | Fujifilm Corporation | Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye composition, and oxide semiconductor electrode |
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Application publication date: 20140326 |