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 PDF

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Publication number
CN108550468A
CN108550468A CN201810184158.7A CN201810184158A CN108550468A CN 108550468 A CN108550468 A CN 108550468A CN 201810184158 A CN201810184158 A CN 201810184158A CN 108550468 A CN108550468 A CN 108550468A
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dye
film
solar cell
film solar
tio
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朱凯
刘锋
李旭倩
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Nanjing Zhengchun Electronic Technology Co Ltd
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Nanjing Zhengchun Electronic Technology Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20Light-sensitive devices
    • H01G9/2059Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20Light-sensitive devices
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/542Dye sensitized solar cells

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  • 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

A kind of codoping modified nanocrystalline TiO for dye-sensitized film solar cell2 Film
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):
CN201810184158.7A 2018-03-07 2018-03-07 A kind of codoping modified nanocrystalline TiO for dye-sensitized film solar cell2Film Withdrawn CN108550468A (en)

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