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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- 239000003446 ligand Substances 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000004065 semiconductor Substances 0.000 claims abstract description 5
- 239000000975 dye Substances 0.000 claims description 41
- 230000001235 sensitizing effect Effects 0.000 claims description 14
- -1 alkyl carboxylic acid Chemical class 0.000 claims description 11
- 239000003086 colorant Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- 239000010410 layer Substances 0.000 claims description 6
- 238000004873 anchoring Methods 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000002209 hydrophobic effect Effects 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 241000555268 Dendroides Species 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical class 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- 150000001413 amino acids Chemical class 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 230000000994 depressogenic effect Effects 0.000 claims description 2
- 230000005595 deprotonation Effects 0.000 claims description 2
- 238000010537 deprotonation reaction Methods 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000464 lead oxide Inorganic materials 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 239000003495 polar organic solvent Substances 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims 2
- 239000013110 organic ligand Substances 0.000 claims 2
- 229910018828 PO3H2 Inorganic materials 0.000 claims 1
- DPXGCVSQPPJYRS-UHFFFAOYSA-N S(O)(O)(=O)=O.[C-]#N Chemical compound S(O)(O)(=O)=O.[C-]#N DPXGCVSQPPJYRS-UHFFFAOYSA-N 0.000 claims 1
- 150000001721 carbon Chemical group 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 10
- 238000013461 design Methods 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 4
- 239000004408 titanium dioxide Substances 0.000 abstract description 4
- 230000003595 spectral effect Effects 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 206010070834 Sensitisation Diseases 0.000 description 15
- 230000008313 sensitization Effects 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FXPLCAKVOYHAJA-UHFFFAOYSA-N 2-(4-carboxypyridin-2-yl)pyridine-4-carboxylic acid Chemical compound OC(=O)C1=CC=NC(C=2N=CC=C(C=2)C(O)=O)=C1 FXPLCAKVOYHAJA-UHFFFAOYSA-N 0.000 description 1
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- FBIYTZTWTCPQBF-UHFFFAOYSA-M chlororuthenium(1+) Chemical compound [Ru+]Cl FBIYTZTWTCPQBF-UHFFFAOYSA-M 0.000 description 1
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical class C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 125000001518 isoselenocyanato group Chemical group *N=C=[Se] 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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- Photovoltaic Devices (AREA)
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.
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.
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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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 |
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2012
- 2012-09-26 CN CN201210363431.5A patent/CN103665047A/en active Pending
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