CN101976609B - Method for modulating Fermi level of optical anode of dye sensitized solar cell through trace N-type doping - Google Patents

Method for modulating Fermi level of optical anode of dye sensitized solar cell through trace N-type doping Download PDF

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Publication number
CN101976609B
CN101976609B CN201010505592A CN201010505592A CN101976609B CN 101976609 B CN101976609 B CN 101976609B CN 201010505592 A CN201010505592 A CN 201010505592A CN 201010505592 A CN201010505592 A CN 201010505592A CN 101976609 B CN101976609 B CN 101976609B
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trace
solar cell
fermi level
sensitized solar
type doping
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CN101976609A (en
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赵兴中
彭涛
陈博磊
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Wuhan University WHU
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Wuhan University WHU
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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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention discloses a method for modulating Fermi level of an optical anode of a dye sensitized solar cell through trace N-type doping, which comprises the steps of: with a salt containing a +5 valence or +6 valence metal element is used as an N type doping source material, preparing trace N type doped titanium dioxide slurry by adopting a hydrothermal method and preparing a trace N type doped titanium dioxide nanocrystalline porous film electrode by adopting a coating method. The Fermi level of titanium dioxide nano particles is modulated through trace N type doping, which can remarkably improve the open-circuit voltage, the short-circuit current and the photoelectricity conversion efficiency of the dye sensitized solar cell. Meanwhile, the invention has the advantages of low cost, simple process and good repeatability, and is suitable for industrialized application.

Description

A kind of trace N type mixes and modulates the method for dye-sensitized solar cell anode Fermi level
Technical field
The invention belongs to the technical field of photovoltaic cell, relate to a kind of preparation method of dye-sensitized solar cell anode.
Background technology
The present peak efficiency of reporting of DSSC still has big gap with its theoretical value about 11%.The photoelectric conversion efficiency of DSSC depends primarily on short circuit current, open circuit voltage and the fill factor, curve factor of battery.Yet, research to DSSC at present mainly concentrates on solid electrolyte or quasi-solid electrolyte replacement liquid electrolyte, the development of new dyestuff makes the spectrum coverage rate be extended to near-infrared region from visible region, studies novel laminated tandem battery structure etc.For porous TiO as the DSSC basic framework 2The broadband semiconductor film removes a small amount of research and explores raising porous TiO 2Outside the conductivity of film, for by mix modulation broadband semiconductor Fermi level and it to the influence of dye sensitization broadband semiconductor solar cell properties almost also nobody explore.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of new mixing with trace N type to modulate the method for dye-sensitized solar cell anode Fermi level.
Technical solution of the present invention is: with contain+5 valencys or+salt of 6 valency metallic elements is as N type doped source material, and is titania-doped, uses the Hydrothermal Preparation titania slurry, prepares the titanium dioxide nanocrystalline porous film electrode with coating method.
N type titanium dioxide nanocrystalline porous membrane and transparent conductive substrate are formed the anode of DSSC.
The preparation method of aforesaid DSSC doped electrode is characterized in that: doping ratio (+5 valencys or+atomic ratio of 6 valency metallic elements and titanium elements) is 1 ~ 100ppm.
With the prepared N type doped electrode of N719 dye sensitization the present invention, and drip redox electrolytes matter on this N type doped electrode, add a cover electrode is assembled into DSSC.
Redox electrolytes plasmogamy ratio in the such scheme is: 0.1mol/L 1-propy-3-methylimidazolium iodide (1-propyl group-3-methylimidazole iodine), 0.05mol/L LiI, 0.1mol/L GNCS, 0.03mol/L I2,0.5mol/L 4-tert-butylpridine (4-tert .-butylpyridine), solvent are the mixed solution (volume ratio is 1:1) of propene carbonate and acetonitrile.
The invention provides a kind of the doping and modulate broadband semiconductor titania nanoparticles Fermi level, and then prepare the method for DSSC N type doped electrode by trace N type.This doped electrode can significantly improve the open circuit voltage of battery simultaneously, and short circuit current is a kind of effective ways that improve the DSSC electricity conversion.
Advantage of the present invention is: preparation technology is with low cost for this method, and technology is simple, good reproducibility.Because trace N type mixes not only can increase the carrier concentration of titanium dioxide semiconductor nano particle, improve semi-conductive transport property, and can improve the Fermi level of titanium dioxide semiconductor nano particle simultaneously, therefore, the short circuit current of DSSC and open circuit voltage all can be improved simultaneously, and then improve the electricity conversion of DSSC.
Embodiment
Embodiment one
1. get and pour in the 50ml water after 10ml isopropyl titanate and 2.1g acetic acid mix, stirred 1 hour under the room temperature, afterwards, add 0.68ml nitric acid, be warming up to 80 ℃ of dispergation.
2. in the dispergation process, press the molybdenum titanium atom, in colloidal sol, add ammonium molybdate aqueous solution than for 5ppm.
3. dispergation was 63ml with the colloidal sol constant volume after 3 hours, poured in the water heating kettle liner, was incubated 12 hours down at 230 ℃.
4. take out the sediment in the water heating kettle liner, drip the nitric acid of 0.4ml, stirred 30 minutes under the room temperature, afterwards, move in the Ultrasound Instrument, the setting ultrasonic power is 200W, ultrasonic 30 minutes, afterwards, revolve and steam to 20ml, and add 0.56g polyethylene glycol and 0.5ml Triton X-100, stirred 12 hours.
5. the slurry with 4 gained is coated onto on the FTO electro-conductive glass, is incubated 30 minutes down at 500 ℃, obtains mixing the titanium dioxide electrodes of molybdenum.
6. use the prepared doped electrode of N719 dye sensitization the present invention, and drip redox electrolytes matter on this doped electrode, add a cover electrode is assembled into DSSC.
7. photovoltaic energy conversion efficiency measurement:
Test condition: 500W simulated solar radiant xenon lamp (Oriel 91192, USA), Keithly 2400 source meter, irradiation intensity is 100W/cm 2, it is 0. 25cm that battery is subjected to illuminating area 2Test result: open circuit voltage V OcBe 715mV, short-circuit current density J ScBe 12.30 mA/cm 2, electricity conversion is 6.00%.
Embodiment two
1. as described in the enforcement scheme one.
2. in the dispergation process, press the molybdenum titanium atom, in colloidal sol, add ammonium molybdate aqueous solution than for 10ppm.
3 ~ 6 as described in the enforcement scheme one.
7. photovoltaic energy conversion efficiency measurement:
Test condition: 500W simulated solar radiant xenon lamp (Oriel 91192, USA), Keithly 2400 source meter, irradiation intensity is 100W/cm 2, it is 0.25cm that battery is subjected to illuminating area 2Test result: open circuit voltage V OcBe 735mV, short-circuit current density J ScBe 13.69 mA/cm 2, electricity conversion is 6.89%.
Embodiment three
1. as described in the enforcement scheme one.
2. in the dispergation process, press the molybdenum titanium atom, in colloidal sol, add ammonium molybdate aqueous solution than for 100ppm.
3 ~ 6 as described in the enforcement scheme one.
7. photovoltaic energy conversion efficiency measurement:
Test condition: 500W simulated solar radiant xenon lamp (Oriel 91192, USA), Keithly 2400 source meter, irradiation intensity is 100W/cm 2, it is 0.25cm that battery is subjected to illuminating area 2Test result: open circuit voltage V OcBe 675mV, short-circuit current density J ScBe 12.20 mA/cm 2, electricity conversion is 5.50%.
Embodiment four
1. as described in the enforcement scheme one.
2. in the dispergation process, by tungsten titanium atom ratio be 1,000,000/, in colloidal sol, add ammonium metatungstate solution.
3 ~ 6 as described in the enforcement scheme one.
7. photovoltaic energy conversion efficiency measurement:
Test condition: 500W simulated solar radiant xenon lamp (Oriel 91192, USA), Keithly 2400 source meter, irradiation intensity is 100W/cm 2, it is 0.25cm that battery is subjected to illuminating area 2Test result: open circuit voltage V OcBe 700mV, short-circuit current density J ScBe 12.57mA/cm 2, electricity conversion is 5.44%.
Embodiment five
1. as described in the enforcement scheme one.
2. in the dispergation process, be 2/100000ths, in colloidal sol, add ammonium metatungstate solution by tungsten titanium atom ratio.
3 ~ 6 as described in the enforcement scheme one.
7. photovoltaic energy conversion efficiency measurement:
Test condition: 500W simulated solar radiant xenon lamp (Oriel 91192, USA), Keithly 2400 source meter, irradiation intensity is 100W/cm 2, it is 0.25cm that battery is subjected to illuminating area 2Test result: open circuit voltage V OcBe 685mV, short-circuit current density J ScBe 15.10mA/cm 2, electricity conversion is 7.13%.

Claims (2)

1. a trace N type mixes and modulates the method for dye-sensitized solar cell anode Fermi level, use the Hydrothermal Preparation titania slurry, prepare the titanium dioxide nanocrystalline porous film electrode with coating method, it is characterized in that: with contain+5 valencys or+salt of 6 valency metallic elements is as trace N type doped source material, and is titania-doped; Described+5 valencys or+6 valency metallic elements are tungsten and molybdenum.
2. the preparation method of trace N type dopant dye sensitization solar battery anode as claimed in claim 1 is characterized in that :+5 valencys or+atomic ratio of 6 valency metallic elements and titanium elements is 1～100ppm.
CN201010505592A 2010-10-13 2010-10-13 Method for modulating Fermi level of optical anode of dye sensitized solar cell through trace N-type doping Expired - Fee Related CN101976609B (en)

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