CN108417397A - A kind of polymer dielectric and its application for dye sensitization of solar hull cell - Google Patents
A kind of polymer dielectric and its application for dye sensitization of solar hull cell Download PDFInfo
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- CN108417397A CN108417397A CN201810186014.5A CN201810186014A CN108417397A CN 108417397 A CN108417397 A CN 108417397A CN 201810186014 A CN201810186014 A CN 201810186014A CN 108417397 A CN108417397 A CN 108417397A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- 206010070834 Sensitisation Diseases 0.000 title claims abstract description 15
- 230000008313 sensitization Effects 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 11
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 11
- 239000011521 glass Substances 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 17
- NMGYKLMMQCTUGI-UHFFFAOYSA-J diazanium;titanium(4+);hexafluoride Chemical compound [NH4+].[NH4+].[F-].[F-].[F-].[F-].[F-].[F-].[Ti+4] NMGYKLMMQCTUGI-UHFFFAOYSA-J 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 13
- 229940073608 benzyl chloride Drugs 0.000 claims description 13
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 claims description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004327 boric acid Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012279 sodium borohydride Substances 0.000 claims description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 101710134784 Agnoprotein Proteins 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 5
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- -1 Hexafluoro Titanium Chemical compound 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N methyl phenyl ether Natural products COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 241000549556 Nanos Species 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 23
- 230000035484 reaction time Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 230000002186 photoactivation Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910001510 metal chloride Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- HOGKYJGTZSXWFI-UHFFFAOYSA-N 2,2-bis(1h-pyrazol-5-yl)acetic acid Chemical class C=1C=NNC=1C(C(=O)O)C1=CC=NN1 HOGKYJGTZSXWFI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2004—Light-sensitive devices characterised by the electrolyte, e.g. comprising an organic electrolyte
- H01G9/2009—Solid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors
- H10K30/65—Light-sensitive field-effect devices, e.g. phototransistors
-
- 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
-
- 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
- Y02E10/549—Organic PV cells
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The present invention provides a kind of polymer dielectric for dye sensitization of solar hull cell, the polymer dielectric includes porous polymer and the lithium salts that is filled in porous polymer.The present invention also provides a kind of dye-sensitized film solar cells, include successively from bottom to top：Vacuum glass layer；Conductive glass layer；Adsorb the nanocrystalline TiO of dye sensitizing agent2Film layer；Electrolyte layer；To electrode layer.Polymer dielectric stability provided by the invention is good, electrochemically stable electrochemical window mouth width, can greatly improve the photoelectric conversion efficiency of battery.Dye-sensitized film solar cell mobility provided by the invention is high, energy conversion rate is high, stability is good, durability is good, long lifespan.
Description
Technical field
The invention belongs to photovoltaic material fields, more particularly to a kind of polymer for dye sensitization of solar hull cell
Electrolyte and its application and application.
Background technology
With becoming increasingly conspicuous for energy shortages in global range and environmental issue, the utilization of regenerative resource causes widely
Pay attention to.For photovoltaic generation as a kind of important renewable energy forms, it is technology on the largest scaleization in current regenerative resource
One of the generation mode of exploit condition and commercialized development foreground, has been to be concerned by more and more people.In the past few decades, the sun
The manufacturing industry scale of energy solar panel expands rapidly.2013, the growth rate of U.S.'s solar energy industry was up to 116%, in new energy
It is leading in technical field." star of the solar energy " installed capacity of U.S.'s solar energy power generating project is up to 1.5 ten thousand kW；Japan
SANYO solar energy Noah's ark generated outputs reach 630kW, annual 530000 kWh that generate electricity；Shenzhen world landscape flower that the country is built up is rich
Garden grid-connected photovoltaic system installed capacity of looking at reaches 1MW, has come into operation at present.
Earliest photovoltaic effect is that Edmund Bequerel had found in 1839, after more than 100 years (1954), with
The development of silicon semiconductor industry, first solar cell that can be used for actual power just come out in AT＆T Labs.This is too
Positive energy battery is based on the p-n junction of silicon semiconductor, electricity conversion 6%.
Organic solar batteries constantly attract more people as a kind of novel battery with its exclusive feature
Put into the research and development in this field.The fast of its development speed also has benefited from its exclusive advantage and characteristic, such as：
It is all preferable that organic material synthesis cost is low, function is easy to modulation, flexibility and film forming；Process is relatively easy, can low temperature
Operation, element manufacturing cost are relatively low；Large area manufacture can be achieved, flexible substrate can be used, is environmental-friendly, light portable etc..
Certain existing organic solar material still has many disadvantages：Material mobility is low, high bulk resistor, so as to cause energy conversion rate
It is low；The stability and durability of material are not good enough, and battery life is short.
Invention content
Technical problem：In order to solve the defects of prior art, it is thin for dye sensitization of solar that the present invention provides one kind
The polymer dielectric of film battery and its application.
Technical solution：A kind of polymer dielectric for dye sensitization of solar hull cell provided by the invention, institute
It includes porous polymer and the lithium salts that is filled in porous polymer to state polymer dielectric.
As an improvement, the porous polymer is the polymer of benzyl chloride and bis- (methoxy) benzene of Isosorbide-5-Nitrae-.
As a further improvement, the preparation method of the benzyl chloride and the polymer of bis- (methoxy) benzene of Isosorbide-5-Nitrae-, packet
Include following steps：Under nitrogen protection, by molar ratio (1-2)：1：Bis- (methoxy) benzene of benzyl chloride, 1,4- of (2-4), trichlorine
Change iron to be added in organic solvent, stir evenly, 10-12h is reacted at 85-95 DEG C, it is cooling, be filtered, washed, dry to get.
It is improved as another kind, the lithium salts is LiClO4。
The present invention also provides a kind of dye-sensitized film solar cells, include successively from bottom to top：
(1) vacuum glass layer；
(2) conductive glass layer；
(3) the nanocrystalline TiO of dye sensitizing agent is adsorbed2Film layer；
(4) electrolyte layer；Filling Claims 1-4 any one of them is used for dye sensitization too in the electrolyte layer
The polymer dielectric of positive energy hull cell；
(5) to electrode layer.
As an improvement, the nanocrystalline TiO2Film layer is the nanocrystalline TiO of modification2Film, the modification it is nanocrystalline
TiO2Film is nano silver and La co-doped nano crystalline substances TiO2Film.
As a further improvement, the nano silver and La co-doped nano crystalline substances TiO2The preparation method of film is：
(1) in ice-water bath, stirring is simultaneously by 1.0 × 10-3The AgNO of mol/L3Aqueous solution is added dropwise 2.0 × 10-3mol/L
NaBH4To get Nano silver solution in aqueous solution；
(2) La is configured2O3Suspension, and be added dropwise in the Nano silver solution of step (1), shading standing 10min, then
5-10min is exposed under simulated solar light source, is stood, is removed supernatant liquor；
(3) boric acid and ammonium hexa-fluorotitanate mixed solution are configured, the sediment of step (2) is added, reacts 1-2h, stands, goes
Fall supernatant liquor；
(4) step (3) product is dried, and is heated up with 5 DEG C/min rates, at 400 DEG C of temperature annealing 40-60min to get.
In step (1), AgNO3Aqueous solution and NaBH4The volume ratio of aqueous solution is 1:(1-1.2).
In step (2), La2O3And AgNO3Molar ratio be 1:(4-6).
In step (3), the molar ratio of boric acid and ammonium hexa-fluorotitanate is that the molar ratio of boric acid and ammonium hexa-fluorotitanate is (4-6)：
1；Ammonium hexa-fluorotitanate and AgNO3Molar ratio be (3-5)：1.
As an improvement, the dye sensitizing agent is dye sensitizing agent shown in formula (I) or is double-core shown in formula (IV)
Dye sensitizing agent：
Wherein, the preparation method of dye sensitizing agent shown in formula (I), includes the following steps：In the presence of triethylamine, formula
(II) compound and formula (III) compound reaction to get；Reaction equation is：
Preferably, formula (II) compound, formula (III) compound, the molar ratio of triethylamine are 1：(1-1.2)：(2-4), instead
It is room temperature, reaction time 3-5h to answer temperature.
Wherein, the preparation method of double-core dye sensitizing agent shown in formula (IV), includes the following steps：
(1) in the presence of triethylamine, formula (II) compound and formula (III) compound reaction to get；Reaction equation is：
(2) in the presence of 1,1-, bis- pyrazolyl acetic acids, compound, metal chloride back flow reaction described in formula (I) to get；
Reaction equation is：
Wherein, M is metal, and x is charge number.
In step (1), formula (II) compound, formula (III) compound, the molar ratio of triethylamine are 1：(1-1.2)：(2-4),
Reaction temperature is room temperature, reaction time 3-5h.
In step (2), M Ru, Zn, Pr, Nd, Gd, Dy, Ho, Er or Tm.
In step (2), reaction time 120-140h；Bis- pyrazolyl acetic acids of 1,1-, formula (I) compound, metal chloride
Molar ratio is 1：1：(1.2-1.5).
Advantageous effect：Polymer dielectric stability provided by the invention is good, electrochemically stable electrochemical window mouth width, Neng Gou great
The big photoelectric conversion efficiency for improving battery.
Dye-sensitized film solar cell mobility provided by the invention is high, energy conversion rate is high, stability is good, durable
The good, long lifespan of property.
Specific implementation mode
The present invention is further illustrated below.
Embodiment 1-1
The preparation method of dye photoactivation agent, includes the following steps：In the presence of triethylamine, formula (II) compound and formula
(III) compound reaction to get；Reaction equation is：
Wherein, formula (II) compound, formula (III) compound, the molar ratio of triethylamine are 1：1.1：3, reaction temperature is room
Temperature, reaction time 4h.
MS(m/s):482.1。
Embodiment 1-2
The preparation method of dye photoactivation agent, includes the following steps：In the presence of triethylamine, formula (II) compound and formula
(III) compound reaction to get；
Wherein, formula (II) compound, formula (III) compound, the molar ratio of triethylamine are 1：1：2, reaction temperature is room temperature,
Reaction time is 5h.
MS(m/s):482.1。
Embodiment 1-3
The preparation method of dye photoactivation agent, includes the following steps：In the presence of triethylamine, formula (II) compound and formula
(III) compound reaction to get；
Wherein, formula (II) compound, formula (III) compound, the molar ratio of triethylamine are 1：1.2：4, reaction temperature is room
Temperature, reaction time 3h.
MS(m/s):482.1。
Embodiment 2
The preparation method of double-core dye photoactivation agent, includes the following steps：In the presence of 1,1-, bis- pyrazolyl acetic acids, implementation is taken
Compound described in formula (I) made from example 1 and metal chloride back flow reaction to get；Reaction equation is：
A batch double-core dye photoactivation agent is made, condition see the table below.
Embodiment 3-1
For the modified Nano crystalline substance TiO2 films of dye-sensitized film solar cell, the modified Nano crystalline substance TiO2 films
For nano silver and La co-doped nano crystalline substances TiO2Film, preparation method includes the following steps：
(1) in ice-water bath, stirring is simultaneously by 1.0 × 10-3The AgNO of mol/L3Aqueous solution is added dropwise 2.0 × 10-3mol/L
NaBH4To get Nano silver solution in aqueous solution；Wherein, AgNO3Aqueous solution and NaBH4The volume ratio of aqueous solution is 1:1.1；
(2) La is configured2O3Suspension, and be added dropwise in the Nano silver solution of step (1), shading standing 10min, then
8min is exposed under simulated solar light source, is stood, is removed supernatant liquor；Wherein, La2O3And AgNO3Molar ratio be 1:5；
(3) boric acid and ammonium hexa-fluorotitanate mixed solution are configured, the sediment of step (2) is added, reacts 1.5h, stands, goes
Fall supernatant liquor；Wherein, the molar ratio of boric acid and ammonium hexa-fluorotitanate is 5：1；Ammonium hexa-fluorotitanate and AgNO3Molar ratio be 4：1；
(4) step (3) product is dried, and is heated up with 5 DEG C/min rates, at 400 DEG C of temperature annealing 50min to get.
Embodiment 3-2
For the modified Nano crystalline substance TiO2 films of dye-sensitized film solar cell, the modified Nano crystalline substance TiO2 films
For nano silver and La co-doped nano crystalline substances TiO2Film, preparation method includes the following steps：
(1) in ice-water bath, stirring is simultaneously by 1.0 × 10-3The AgNO of mol/L3Aqueous solution is added dropwise 2.0 × 10-3mol/L
NaBH4To get Nano silver solution in aqueous solution；Wherein, AgNO3Aqueous solution and NaBH4The volume ratio of aqueous solution is 1:1；
(2) La is configured2O3Suspension, and be added dropwise in the Nano silver solution of step (1), shading standing 10min, then
10min is exposed under simulated solar light source, is stood, is removed supernatant liquor；Wherein, La2O3And AgNO3Molar ratio be 1:4；
(3) boric acid and ammonium hexa-fluorotitanate mixed solution are configured, the sediment of step (2) is added, reacts 1h, stands, removes
Supernatant liquor；Wherein, the molar ratio of boric acid and ammonium hexa-fluorotitanate is 6：1；Ammonium hexa-fluorotitanate and AgNO3Molar ratio be 5：1；
(4) step (3) product is dried, and is heated up with 5 DEG C/min rates, at 400 DEG C of temperature annealing 40min to get.
Embodiment 3-3
For the modified Nano crystalline substance TiO2 films of dye-sensitized film solar cell, the modified Nano crystalline substance TiO2 films
For nano silver and La co-doped nano crystalline substances TiO2Film, preparation method includes the following steps：
(1) in ice-water bath, stirring is simultaneously by 1.0 × 10-3The AgNO of mol/L3Aqueous solution is added dropwise 2.0 × 10-3mol/L
NaBH4To get Nano silver solution in aqueous solution；Wherein, AgNO3Aqueous solution and NaBH4The volume ratio of aqueous solution is 1:1.2；
(2) La is configured2O3Suspension, and be added dropwise in the Nano silver solution of step (1), shading standing 10min, then
5min is exposed under simulated solar light source, is stood, is removed supernatant liquor；Wherein, La2O3And AgNO3Molar ratio be 1:6；
(3) boric acid and ammonium hexa-fluorotitanate mixed solution are configured, the sediment of step (2) is added, reacts 2h, stands, removes
Supernatant liquor；Wherein, the molar ratio of boric acid and ammonium hexa-fluorotitanate is 4：1；Ammonium hexa-fluorotitanate and AgNO3Molar ratio be 3：1；
(4) step (3) product is dried, and is heated up with 5 DEG C/min rates, at 400 DEG C of temperature annealing 60min to get.
Embodiment 4-1
For the polymer dielectric of dye sensitization of solar hull cell, the polymer dielectric includes porous polymeric
Object and the lithium salts being filled in porous polymer；
The porous polymer is the polymer of benzyl chloride and bis- (methoxy) benzene of 1,4-；The benzyl chloride and 1,4-
The preparation method of the polymer of bis- (methoxy) benzene, includes the following steps：Under nitrogen protection, by molar ratio 1.5：1：3
Bis- (methoxy) benzene of benzyl chloride, Isosorbide-5-Nitrae-, ferric trichloride are added in organic solvent, stir evenly, 11h is reacted at 90 DEG C, cold
But, be filtered, washed, dry to get；
The lithium salts is LiClO4。
Embodiment 4-2
For the polymer dielectric of dye sensitization of solar hull cell, the polymer dielectric includes porous polymeric
Object and the lithium salts being filled in porous polymer；
The porous polymer is the polymer of benzyl chloride and bis- (methoxy) benzene of 1,4-；The benzyl chloride and 1,4-
The preparation method of the polymer of bis- (methoxy) benzene, includes the following steps：Under nitrogen protection, by molar ratio 1：1：4 chlorine
Change benzyl, bis- (methoxy) benzene of Isosorbide-5-Nitrae-, ferric trichloride to be added in organic solvent, stirs evenly, 10h is reacted at 95 DEG C, it is cooling,
Be filtered, washed, dry to get；
The lithium salts is LiClO4。
Embodiment 4-3
For the polymer dielectric of dye sensitization of solar hull cell, the polymer dielectric includes porous polymeric
Object and the lithium salts being filled in porous polymer；
The porous polymer is the polymer of benzyl chloride and bis- (methoxy) benzene of 1,4-；The benzyl chloride and 1,4-
The preparation method of the polymer of bis- (methoxy) benzene, includes the following steps：Under nitrogen protection, by molar ratio 2：1：2 chlorine
Change benzyl, bis- (methoxy) benzene of Isosorbide-5-Nitrae-, ferric trichloride to be added in organic solvent, stirs evenly, 12h is reacted at 85 DEG C, it is cooling,
Be filtered, washed, dry to get；
The lithium salts is LiClO4。
Embodiment 5
Using the raw material of embodiment 1 to 4, a collection of dye-sensitized film solar cell is prepared, includes successively from bottom to top：
(1) vacuum glass layer；
(2) conductive glass layer；
(3) the nanocrystalline TiO of dye sensitizing agent is adsorbed2Film layer；
(4) electrolyte layer；
(5) to electrode layer.
Raw material sources and in 100mW/cm2Cell photoelectric transfer efficiency see the table below.
Remaining raw material is commercially available.
Claims (9)
1. a kind of polymer dielectric for dye sensitization of solar hull cell, it is characterised in that：The polymer electrolytic
Matter includes porous polymer and the lithium salts that is filled in porous polymer.
2. a kind of polymer dielectric for dye sensitization of solar hull cell according to claim 1, feature
It is：The porous polymer is the polymer of benzyl chloride and bis- (methoxy) benzene of 1,4-.
3. a kind of polymer dielectric for dye sensitization of solar hull cell according to claim 2, feature
It is：The preparation method of the benzyl chloride and the polymer of bis- (methoxy) benzene of Isosorbide-5-Nitrae-, includes the following steps：Nitrogen protection
Under, by molar ratio (1-2)：1：Bis- (methoxy) benzene of benzyl chloride, Isosorbide-5-Nitrae-, the ferric trichloride of (2-4) are added in organic solvent,
Stir evenly, 10-12h reacted at 85-95 DEG C, it is cooling, be filtered, washed, dry to get.
4. a kind of polymer dielectric for dye sensitization of solar hull cell according to claim 1, feature
It is：The lithium salts is LiClO4。
5. a kind of dye-sensitized film solar cell, it is characterised in that：Include successively from bottom to top：
(1) vacuum glass layer；
(2) conductive glass layer；
(3) the nanocrystalline TiO of dye sensitizing agent is adsorbed2Film layer；
(4) electrolyte layer；Filling Claims 1-4 any one of them is used for dye sensitization of solar in the electrolyte layer
The polymer dielectric of hull cell；
(5) to electrode layer.
6. a kind of dye-sensitized film solar cell according to claim 5, it is characterised in that：The nanocrystalline TiO2
Film layer is the nanocrystalline TiO of modification2Film, the nanocrystalline TiO of the modification2Film is that nano silver and La co-doped nanos are brilliant
TiO2Film.
7. a kind of dye-sensitized film solar cell according to claim 6, it is characterised in that：The nano silver and La
Co-doped nano crystalline substance TiO2The preparation method of film is：
(1) in ice-water bath, stirring is simultaneously by 1.0 × 10-3The AgNO of mol/L3Aqueous solution is added dropwise 2.0 × 10-3mol/L
NaBH4To get Nano silver solution in aqueous solution；
(2) La is configured2O3Suspension, and be added dropwise in the Nano silver solution of step (1), shading stands 10min, then is simulating
5-10min is exposed under solar source, is stood, is removed supernatant liquor；
(3) boric acid and ammonium hexa-fluorotitanate mixed solution are configured, the sediment of step (2) is added, reacts 1-2h, is stood, remove on
Layer clear liquid；
(4) step (3) product is dried, and is heated up with 5 DEG C/min rates, at 400 DEG C of temperature annealing 40-60min to get.
8. a kind of dye-sensitized film solar cell according to claim 7, it is characterised in that：In step (1), AgNO3
Aqueous solution and NaBH4The volume ratio of aqueous solution is 1:(1-1.2)；In step (2), La2O3And AgNO3Molar ratio be 1:(4-
6)；In step (3), the molar ratio of boric acid and ammonium hexa-fluorotitanate is that the molar ratio of boric acid and ammonium hexa-fluorotitanate is (4-6)：1；Hexafluoro
Titanium acid ammonium and AgNO3Molar ratio be (3-5)：1.
9. a kind of dye-sensitized film solar cell according to claim 5, it is characterised in that：The dye sensitizing agent
For dye sensitizing agent shown in formula (I) or it is double-core dye sensitizing agent shown in formula (IV)：
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