CN108550468A - A kind of codoping modified nanocrystalline TiO for dye-sensitized film solar cell2Film - Google Patents
A kind of codoping modified nanocrystalline TiO for dye-sensitized film solar cell2Film Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003792 electrolyte Substances 0.000 claims abstract description 8
- 239000011521 glass Substances 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 6
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 31
- 229920000642 polymer Polymers 0.000 claims description 26
- 239000007864 aqueous solution Substances 0.000 claims description 20
- 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 17
- 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 15
- 229940073608 benzyl chloride Drugs 0.000 claims description 15
- 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
- 239000000243 solution Substances 0.000 claims description 11
- UIMPAOAAAYDUKQ-UHFFFAOYSA-N 1-methoxy-4-(4-methoxyphenyl)benzene Chemical group C1=CC(OC)=CC=C1C1=CC=C(OC)C=C1 UIMPAOAAAYDUKQ-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910000421 cerium(III) oxide Inorganic materials 0.000 claims description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 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
- 101710134784 Agnoprotein Proteins 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 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
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 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
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920000867 polyelectrolyte Polymers 0.000 claims description 4
- OGUZWZRDBPUXAK-UHFFFAOYSA-N 5,5-dimethoxy-2-phenylcyclohexa-1,3-diene Chemical group C1=CC(OC)(OC)CC=C1C1=CC=CC=C1 OGUZWZRDBPUXAK-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 7
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 36
- 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
- 206010070834 Sensitisation Diseases 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910001510 metal chloride Inorganic materials 0.000 description 3
- 239000003504 photosensitizing agent Substances 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000002186 photoactivation 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
- 238000012546 transfer Methods 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
- 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 239000010409 thin film Substances 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
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
A kind of codoping modified nanocrystalline TiO2 films for dye-sensitized film solar cell provided by the invention, the nanocrystalline TiO2Film layer is the nanocrystalline TiO of modification2Film, the nanocrystalline TiO of the modification2Film is nano silver, La, Ce co-doped nano crystalline substance TiO2Film.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.Modified Nano crystalline substance TiO provided by the invention2Film can reduce the transmission path of electronics in the film, reduce recombination probability, porosity is big, is conducive to transmission of the electrolyte in the material of hole, substantially increases 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 codope for dye-sensitized film solar cell
Modified Nano crystalline substance TiO2 films.
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.
One of an important factor for nanocrystalline TiO2 films are influence organic solar batteries performances.
Invention content
Technical problem:In order to solve the defects of prior art, the present invention provides one kind being used for the dye-sensitized film sun
The codoping modified nanocrystalline TiO2 films of energy battery.
Technical solution:It is provided by the invention a kind of for the codoping modified nanocrystalline of dye-sensitized film solar cell
TiO2 films, the nanocrystalline TiO2Film layer is the nanocrystalline TiO of modification2Film, the nanocrystalline TiO of the modification2Film is
Nano silver, La, Ce co-doped nano crystalline substance TiO2Film.
As an improvement, the nano silver, La, Ce codope 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 configured2O3、Ce2O3Suspension, and be added dropwise in the Nano silver solution of step (1), shading is stood
10min, then 5-10min is exposed under simulated solar light source, it stands, removes 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), La2O3、Ce2O3And AgNO3Molar ratio be 1:(0.3-0.5):(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.
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 TiO2 film layers of dye sensitizing agent are adsorbed;The nanocrystalline TiO2Film layer is above-mentioned for contaminating
The codoping modified nanocrystalline TiO2 films of material sensitization thin-film solar cells;
(4) electrolyte layer;
(5) to electrode layer.
As an improvement, the electrolyte layer is polyelectrolyte floor, the polyelectrolyte floor includes porous polymeric
Object and the lithium salts being filled in porous polymer.
As a further improvement, the porous polymer is benzyl chloride and 4, the polymerization of bis- (methoxy) biphenyl of 4`-
Object;The benzyl chloride and 4, the preparation method of the polymer of bis- (methoxy) biphenyl of 4`-, includes the following steps:Nitrogen is protected
Under shield, by molar ratio (1-2):1:Bis- (methoxy) biphenyl of benzyl chloride, 4,4`-, the ferric trichloride of (2-4) are added organic molten
In agent, stir evenly, react at room temperature 10-12h, it is cooling, be filtered, washed, dry to get;The lithium salts is LiClO4。
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:Modified Nano crystalline substance TiO provided by the invention2Film can reduce the transmission road of electronics in the film
Diameter reduces recombination probability, and porosity is big, is conducive to transmission of the electrolyte in the material of hole, substantially increases the photoelectricity of battery
Transfer efficiency.
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 new dye photosensitizer, 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/z):559.2。
Embodiment 1-2
The preparation method of new dye photosensitizer, 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 3h.
MS(m/z):559.2。
Embodiment 1-3
The preparation method of new dye photosensitizer, 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 5h.
MS(m/z):559.2。
Embodiment 2
The preparation method of new double-core dye photoactivation agent, includes the following steps:In the presence of 1,1-, bis- pyrazolyl acetic acids, formula
(I) compound, metal chloride back flow reaction described in 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 configured2O3、Ce2O3Suspension, and be added dropwise in the Nano silver solution of step (1), shading is stood
10min, then 10min is exposed under simulated solar light source, it stands, removes supernatant liquor;Wherein, La2O3、Ce2O3And AgNO3Rub
You are than being 1:0.4:5;
(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 configured2O3、Ce2O3Suspension, and be added dropwise in the Nano silver solution of step (1), shading is stood
10min, then 10min is exposed under simulated solar light source, it stands, removes supernatant liquor;Wherein, La2O3、Ce2O3And AgNO3Rub
You are than being 1:0.3:4;
(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 configured2O3、Ce2O3Suspension, and be added dropwise in the Nano silver solution of step (1), shading is stood
10min, then 10min is exposed under simulated solar light source, it stands, removes supernatant liquor;Wherein, La2O3、Ce2O3And AgNO3Rub
You are than being 1:0.5:6;
(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) biphenyl of 4,4`-;The benzyl chloride with
The preparation method of the polymer of 4,4`- bis- (methoxy) biphenyl, includes the following steps:Under nitrogen protection, by molar ratio
1.5: 1:3 benzyl chloride, bis- (methoxy) biphenyl of 4,4`-, ferric trichloride are added in organic solvent, stir evenly, room temperature
React 11h, it is cooling, 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) biphenyl of 4,4`-;The benzyl chloride with
The preparation method of the polymer of 4,4`- bis- (methoxy) biphenyl, includes the following steps:Under nitrogen protection, by molar ratio 1:
1:4 benzyl chloride, bis- (methoxy) biphenyl of 4,4`-, ferric trichloride are added in organic solvent, stir evenly, and react at room temperature
12h, 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) biphenyl of 4,4`-;The benzyl chloride with
The preparation method of the polymer of 4,4`- bis- (methoxy) biphenyl, includes the following steps:Under nitrogen protection, by molar ratio 2:
1:2 benzyl chloride, bis- (methoxy) biphenyl of 4,4`-, ferric trichloride are added in organic solvent, stir evenly, and react at room temperature
10h, 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 codoping modified nanocrystalline TiO2 films for dye-sensitized film solar cell, it is characterised in that:Institute
State nanocrystalline TiO2Film layer is the nanocrystalline TiO of modification2Film, the nanocrystalline TiO of the modification2Film be nano silver, La,
Ce co-doped nano crystalline substances TiO2Film.
2. a kind of codoping modified nanocrystalline TiO2 for dye-sensitized film solar cell according to claim 1
Film, it is characterised in that:The nano silver, La, Ce codope 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 configured2O3、Ce2O3Suspension, 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, 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.
3. a kind of dye-sensitized film solar cell according to claim 2, it is characterised in that:In step (1), AgNO3
Aqueous solution and NaBH4The volume ratio of aqueous solution is 1:(1-1.2).
4. a kind of dye-sensitized film solar cell according to claim 2, it is characterised in that:In step (2),
La2O3、Ce2O3And AgNO3Molar ratio be 1:(0.3-0.5):(4-6).
5. a kind of dye-sensitized film solar cell according to claim 2, it is characterised in that:In step (3), boric acid
Molar ratio with ammonium hexa-fluorotitanate is that the molar ratio of boric acid and ammonium hexa-fluorotitanate is (4-6):1;Ammonium hexa-fluorotitanate and AgNO3Rub
You are than being (3-5):1.
6. 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 TiO2 film layers of dye sensitizing agent are adsorbed;The nanocrystalline TiO2Film layer is that claim 1 to 5 is any
The codoping modified nanocrystalline TiO2 films for dye-sensitized film solar cell described in;
(4) electrolyte layer;
(5) to electrode layer.
7. a kind of dye-sensitized film solar cell according to claim 6, it is characterised in that:The electrolyte layer is
Polyelectrolyte floor, the polyelectrolyte floor include porous polymer and the lithium salts that is filled in porous polymer.
8. a kind of dye-sensitized film solar cell according to claim 7, it is characterised in that:The porous polymer
For the polymer of benzyl chloride and bis- (methoxy) biphenyl of 4,4`-;The benzyl chloride and bis- (methoxy) biphenyl of 4,4`-
Polymer preparation method, include the following steps:Under nitrogen protection, by molar ratio (1-2):1:The benzyl chloride of (2-4), 4,4
Bis- (methoxy) biphenyl of `-, ferric trichloride are added in organic solvent, stir evenly, and react at room temperature 10-12h, cooling, mistake
Filter, washing, it is dry to get;The lithium salts is LiClO4。
9. a kind of dye-sensitized film solar cell according to claim 6, 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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