CN102623190A - Method for improving photoelectric conversion efficiency of dye sensitized solar cell - Google Patents

Method for improving photoelectric conversion efficiency of dye sensitized solar cell Download PDF

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CN102623190A
CN102623190A CN2012101142195A CN201210114219A CN102623190A CN 102623190 A CN102623190 A CN 102623190A CN 2012101142195 A CN2012101142195 A CN 2012101142195A CN 201210114219 A CN201210114219 A CN 201210114219A CN 102623190 A CN102623190 A CN 102623190A
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photoelectric conversion
conversion efficiency
dssc
solar cell
sensitized solar
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赵兴中
梁亮亮
刘钰旻
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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
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells

Abstract

The invention discloses a method for improving the photoelectric conversion efficiency of a dye sensitized solar cell. According to the method, inorganic salt containing +2 or +3 valent metal elements is taken as a P-type doping source to dope a titanium dioxide nano porous film photoanode, the carrier concentration and conductivity in a titanium dioxide nano porous film can be improved, and when the trace P-type doped titanium dioxide nano porous film is used for a photoanode of the dye sensitized solar cell, the short-circuit current of the dye sensitized solar cell can be effectively improved and the photoelectric conversion efficiency of the dye sensitized solar cell is improved further.

Description

A kind of method that improves the DSSC photoelectric conversion efficiency
Technical field
The invention belongs to the dye-sensitized solar cell anode research field, relate to a kind of method that improves the DSSC photoelectric conversion efficiency.
Background technology
DSSC mainly is an imitation photosynthesis principle; A kind of novel solar battery of developing; Its main advantage is: abundant raw materials, cost is low, technology is simple relatively, in the large tracts of land suitability for industrialized production, has bigger advantage, and used raw material and production process all are nontoxic, free of contamination simultaneously; And the part raw material can be reclaimed fully, and the protection human environment is had great importance.The photoelectric conversion efficiency of DSSC depends primarily on short circuit current, open circuit voltage and the fill factor, curve factor of battery.Be reported at present the high-photoelectric transformation efficiency of the DSSC that obtains in the laboratory and be about 12.3%, also had big gap apart from commercial application.
In order to improve the photoelectric conversion efficiency of DSSC; Aspect the light anode of battery; The main light anode that adopts the material of multiple new structures such as nanotube, nanometer rods, nucleocapsid structure as battery, thus improve light induced electron transmission, reduce light induced electron compound, improve the dyestuff adsorption rate.Also have through TiO as battery light anode 2Mix and adjust TiO 2The position of valence band or conduction band, thereby adjustment TiO 2To absorption of visible light zone and change TiO 2Fermi level is realized the adjustment to aspects such as battery open circuit voltages afterwards.At present to TiO as battery light anode 2Doping research in, generally press atomic ratio and in 0.1%～10% scope, add metal or nonmetalloid, through the trace doped TiO that adjusts 2The research of charge carrier number and light anode conductance rate aspect is almost also had no talent and is explored.
Summary of the invention
The purpose of this invention is to provide a kind of method that improves the DSSC photoelectric conversion efficiency; It is trace doped that this method is carried out the P type through the titanium dioxide anode to DSSC; Increasing the carrier concentration and the conductivity of titanium dioxide, thereby significantly improve the short circuit current and the electricity conversion of DSSC.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method that improves the DSSC photoelectric conversion efficiency, this method be with contain+2 or+inorganic salts of 3 valency metallic elements are that P type doped source is mixed to nano titania porous membrane light anode.Concrete grammar is: with contain+2 or+inorganic salts of 3 valency metallic elements are P type doped source, adopt the titania-doped slurry of Hydrothermal Preparation P type, and prepare P type doping titanium dioxide nano porous membrane light anode with coating method.
The addition of above-mentioned doped source is: in the doped source atomicity of metallic element be in the titanium source titanium elements 90/10ths/1000000ths to 1,000,000.Adopting the titanium source in the titania-doped slurry of Hydrothermal Preparation P type is the isopropyl alcohol attitude.
Above-mentioned containing+2 or+inorganic salts of 3 valency metallic elements are nitrate, described nitrate is yttrium nitrate or magnesium nitrate.
The light anode of DSSC is made up of transparent FTO electro-conductive glass and titanium dioxide porous film two parts; Employing the inventive method is carried out the doping of trace P type to titanium dioxide porous film electrode wherein; To improve carrier concentration and conductivity in the titanium dioxide porous film; The titanium dioxide porous film that will pass through the doping of trace P type is used for the light anode of DSSC; Can effectively improve the short circuit current of DSSC, and then improve the electricity conversion of DSSC.
Compared with prior art, the present invention has the following advantages and beneficial effect:
1, the inventive method can effectively improve the short circuit current and the electricity conversion of DSSC;
2, the inventive method adopts the P type doped source of denier can realize significantly improving the short circuit current and the electricity conversion of DSSC, has practiced thrift cost greatly;
3, the inventive method is with low cost, and technology is simple, good reproducibility.
Description of drawings
Fig. 1 is Y 3+The I-V curve chart of the DSSC that mixes;
Fig. 2 is Mg 2+The I-V curve chart of the DSSC that mixes.
Embodiment
To combine embodiment to further specify the present invention below.
Instance 1
1) get 10ml isopropyl titanate and 2.1g glacial acetic acid and mix, ultrasonic 2min mixes it; In conical flask, add the 50mL deionized water, the mixed liquor of isopropyl titanate and glacial acetic acid is poured in the conical flask, stirring is hydrolyzed and polycondensation reaction under the room temperature, in conical flask, adds the 0.68mL red fuming nitric acid (RFNA) after 1 hour, is warming up to 80 degrees centigrade, carries out the dispergation reaction.
2) dispergation carried out the suction filtration operation with colloidal sol after 3 hours, then filtrating was settled to 63ml, poured in the water heating kettle, was warming up to 220 ℃ and carried out hydro-thermal reaction 12 hours.
3) in the hydro-thermal reaction product, drip the 0.4ml red fuming nitric acid (RFNA), stirring at room 15 minutes is put into Ultrasound Instrument; Setting power is 300W; After ultrasonic 30 minutes, rotary distillation to liquor capacity is 20ml, adds 0.56g pore creating material polyethylene glycol and 0.5ml triton x-100 then; Stirring at room 12 hours obtains the hydro-thermal slurry.
4) the hydro-thermal slurry is coated onto on the FTO electro-conductive glass with glass bar,, puts into annealing furnace then, be incubated 30 minutes down, obtain unadulterated titanium dioxide photo anode at 500 ℃ in 60 ℃ of oven dry down.
5) adopt N719 dye sensitization titanium dioxide photo anode, and drip redox electrolytes matter on this doped electrode, add a cover platinum electrode is assembled into DSSC.The redox electrolytes matter that is adopted in this step consists of: 0.1L/mol 1-propyl group-3-methylimidazole iodine, 0.05L/mol LiI, 0.1L/mol guanidine thiocyanate (GuNCS), 0.03L/mol I 2, 0.5L/mol 4-tert .-butylpyridine, solvent is the mixed solution of propene carbonate and acetonitrile, wherein, the volume ratio of propene carbonate and acetonitrile is 1: 1.
6) the photovoltaic energy conversion efficient of measurement gained DSSC:
Test condition: the standard 500W simulated solar irradiation xenon lamp of Oriel 91192 models of the employing U.S. is as light source, and irradiation intensity is 80W/cm 2, it is 0.25cm that battery receives illuminating area 2
Method of measurement: adopt traditional electrical chemistry station battery method of testing to measure the cell I-V curve chart, and from this curve, read open circuit voltage V OC, short-circuit current density J SC, and pass through formula
Figure BDA0000154607540000031
The photoelectric conversion efficiency η of counting cell, in this formula, FF is the fill factor, curve factor of battery,
Figure BDA0000154607540000032
V MaxPairing voltage during for battery power output maximum, J MaxPairing current density during for battery power output maximum point, V MaxAnd J MaxAll can from the I-V curve chart of battery, read P InThe expression incident intensity.
Measurement result: open circuit voltage V OCBe 0.698V, short-circuit current density J SCBe 8.462mA/cm 2, electricity conversion η is 5.176%.
Instance 2
1) get 10ml isopropyl titanate and 2.1g glacial acetic acid and mix, ultrasonic 2min mixes it.By the yttrium atom number is 10/1000000ths of titanium atom number, in conical flask, adds yttrium nitrate aqueous solution, and used yttrium nitrate aqueous solution concentration is 3.275 * 10 -4Mol/L adds deionized water again volume is adjusted to 50mL.The mixed liquor of isopropyl titanate and glacial acetic acid is poured in the conical flask, and stirring is hydrolyzed and polycondensation reaction under the room temperature, in conical flask, adds the 0.68mL red fuming nitric acid (RFNA) after 1 hour, is warming up to 80 degrees centigrade, carries out the dispergation reaction.
2)～5) with the step 2 of embodiment 1)～5).
6) the photovoltaic energy conversion efficient of measurement gained DSSC:
Measure strip spare and method of measurement with embodiment 1.
Measurement result: open circuit voltage V OCBe 0.733V, short-circuit current density J SCBe 8.772mA/cm 2, electricity conversion η is 5.553%.
Instance 3
1) get 10ml isopropyl titanate and 2.1g glacial acetic acid and mix, ultrasonic 2min mixes it.By the yttrium atom number is 1,000,000 of titanium atom number/30, in conical flask, adds yttrium nitrate aqueous solution, and used yttrium nitrate aqueous solution concentration is 3.275 * 10 -4Mol/L adds deionized water again volume is adjusted to 50mL.The mixed liquor of isopropyl titanate and glacial acetic acid is poured in the conical flask, and stirring is hydrolyzed and polycondensation reaction under the room temperature, in conical flask, adds the 0.68mL red fuming nitric acid (RFNA) after 1 hour, is warming up to 80 degrees centigrade, carries out the dispergation reaction.
2)～5) with the step 2 of embodiment 1)～5).
6) the photovoltaic energy conversion efficient of measurement gained DSSC:
Measure strip spare and method of measurement with embodiment 1.
Measurement result: open circuit voltage V OCBe 0.719V, short-circuit current density J SCBe 8.928mA/cm 2, electricity conversion η is 5.648%.
Instance 4
1) get 10ml isopropyl titanate and 2.1g glacial acetic acid and mix, ultrasonic 2min mixes it.By the yttrium atom number is 1,000,000 of titanium atom number/60, in conical flask, adds yttrium nitrate aqueous solution, and used yttrium nitrate aqueous solution concentration is 3.275 * 10 -4Mol/L adds deionized water again volume is adjusted to 50mL.The mixed liquor of isopropyl titanate and glacial acetic acid is poured in the conical flask, and stirring is hydrolyzed and polycondensation reaction under the room temperature, in conical flask, adds the 0.68mL red fuming nitric acid (RFNA) after 1 hour, is warming up to 80 degrees centigrade, carries out the dispergation reaction.
2)～5) with the step 2 of embodiment 1)～5).
6) the photovoltaic energy conversion efficient of measurement gained DSSC:
Measure strip spare and method of measurement with embodiment 1.
Measurement result: open circuit voltage V OCBe 0.716V, short-circuit current density J SCBe 10.662mA/cm 2, electricity conversion η is 6.785%.
Instance 5
1) get 10ml isopropyl titanate and 2.1g glacial acetic acid and mix, ultrasonic 2min mixes it.By the yttrium atom number is 1,000,000 of titanium atom number/90, in conical flask, adds yttrium nitrate aqueous solution, and used yttrium nitrate aqueous solution concentration is 3.275 * 10 -4Mol/L adds deionized water again volume is adjusted to 50mL.The mixed liquor of isopropyl titanate and glacial acetic acid is poured in the conical flask, and stirring is hydrolyzed and polycondensation reaction under the room temperature, in conical flask, adds the 0.68mL red fuming nitric acid (RFNA) after 1 hour, is warming up to 80 degrees centigrade, carries out the dispergation reaction.
2)～5) with the step 2 of embodiment 1)～5).
6) the photovoltaic energy conversion efficient of measurement gained DSSC:
Measure strip spare and method of measurement with embodiment 1.
Measurement result: open circuit voltage V OCBe 0.709V, short-circuit current density J SCBe 9.341mA/cm 2, electricity conversion η is 5.786%.
Instance 6
1) get 10ml isopropyl titanate and 2.1g glacial acetic acid and mix, ultrasonic 2min mixes it.By the magnesium atom number is 10/1000000ths of titanium atom number, in conical flask, adds magnesium nitrate aqueous solution, and used magnesium nitrate aqueous solution concentration is 3.275 * 10 -4Mol/L adds deionized water again volume is adjusted to 50mL.The mixed liquor of isopropyl titanate and glacial acetic acid is poured in the conical flask, and stirring is hydrolyzed and polycondensation reaction under the room temperature, in conical flask, adds the 0.68mL red fuming nitric acid (RFNA) after 1 hour, is warming up to 80 degrees centigrade, carries out the dispergation reaction.
2)～5) with the step 2 of embodiment 1)～5).
6) the photovoltaic energy conversion efficient of measurement gained DSSC:
Measure strip spare and method of measurement with embodiment 1.
Measurement result: open circuit voltage V OCBe 0.704V, short-circuit current density J SCBe 9.152mA/cm 2, electricity conversion η is 5.679%.
Instance 7
1) get 10ml isopropyl titanate and 2.1g glacial acetic acid and mix, ultrasonic 2min mixes it.By the magnesium atom number is 1,000,000 of titanium atom number/20, in conical flask, adds magnesium nitrate aqueous solution, and used magnesium nitrate aqueous solution concentration is 3.275 * 10 -4Mol/L adds deionized water again volume is adjusted to 50mL.The mixed liquor of isopropyl titanate and glacial acetic acid is poured in the conical flask, and stirring is hydrolyzed and polycondensation reaction under the room temperature, in conical flask, adds the 0.68mL red fuming nitric acid (RFNA) after 1 hour, is warming up to 80 degrees centigrade, carries out the dispergation reaction.
2)～5) with the step 2 of embodiment 1)～5).
6) the photovoltaic energy conversion efficient of measurement gained DSSC:
Measure strip spare and method of measurement with embodiment 1.
Measurement result: open circuit voltage V OCBe 0.691V, short-circuit current density J SCBe 10.057mA/cm 2, electricity conversion η is 6.165%.
Instance 8
1) get 10ml isopropyl titanate and 2.1g glacial acetic acid and mix, ultrasonic 2min mixes it.By the magnesium atom number is 1,000,000 of titanium atom number/30, in conical flask, adds magnesium nitrate aqueous solution, and used magnesium nitrate aqueous solution concentration is 3.275 * 10 -4Mol/L adds deionized water again volume is adjusted to 50mL.The mixed liquor of isopropyl titanate and glacial acetic acid is poured in the conical flask, and stirring is hydrolyzed and polycondensation reaction under the room temperature, in conical flask, adds the 0.68mL red fuming nitric acid (RFNA) after 1 hour, is warming up to 80 degrees centigrade, carries out the dispergation reaction.
2)～5) with the step 2 of embodiment 1)～5).
6) the photovoltaic energy conversion efficient of measurement gained DSSC:
Measure strip spare and method of measurement with embodiment 1.
Measurement result: open circuit voltage V OCBe 0.690V, short-circuit current density J SCBe 9.003mA/cm 2, electricity conversion η is 5.499%.
Instance 9
1) get 10ml isopropyl titanate and 2.1 glacial acetic acid and mix, ultrasonic 2min mixes it.By the magnesium atom number is 1,000,000 of titanium atom number/50, in conical flask, adds magnesium nitrate aqueous solution, and used magnesium nitrate aqueous solution concentration is 3.275 * 10 -4Mol/L adds deionized water again volume is adjusted to 50mL.The mixed liquor of isopropyl titanate and glacial acetic acid is poured in the conical flask, and stirring is hydrolyzed and polycondensation reaction under the room temperature, in conical flask, adds the 0.68mL red fuming nitric acid (RFNA) after 1 hour, is warming up to 80 degrees centigrade, carries out the dispergation reaction.
2)～5) with the step 2 of embodiment 1)～5).
6) the photovoltaic energy conversion efficient of measurement gained DSSC:
Measure strip spare and method of measurement with embodiment 1.
Measurement result: open circuit voltage V OCBe 0.685V, short-circuit current density J SCBe 8.762mA/cm 2, electricity conversion η is 5.383%.
Table 1 is the measurement result of embodiment 1～9, from table, can significantly find out, adopting the inventive method is obviously to improve the electricity conversion of DSSC.
Table 1
Figure BDA0000154607540000061

Claims (5)

1. method that improves the DSSC photoelectric conversion efficiency is characterized in that:
With contain+2 or+inorganic salts of 3 valency metallic elements are that P type doped source is mixed to nano titania porous membrane light anode.
2. the method for raising DSSC photoelectric conversion efficiency according to claim 1; It is characterized in that: described with contain+2 or+to be P type doped source to the nano titania porous membrane light anode step of mixing further be for the inorganic salts of 3 valency metallic elements: with contain+2 or+inorganic salts of 3 valency metallic elements are P type doped source; Adopt the titania-doped slurry of Hydrothermal Preparation P type, and prepare P type doping titanium dioxide nano porous membrane light anode with coating method.
3. the method for raising DSSC photoelectric conversion efficiency according to claim 1 and 2 is characterized in that: the addition of said doped source is: in the doped source atomicity of metallic element be in the titanium source titanium elements 90/10ths/1000000ths to 1,000,000.
4. the method for raising DSSC photoelectric conversion efficiency according to claim 1 and 2 is characterized in that: described containing+2 or+inorganic salts of 3 valency metallic elements are nitrate.
5. the method for raising DSSC photoelectric conversion efficiency according to claim 4 is characterized in that: described nitrate is yttrium nitrate or magnesium nitrate.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103560013A (en) * 2013-11-07 2014-02-05 武汉大学 Dye-sensitized solar cell with sulfide counter electrode and preparation method thereof
CN104240957A (en) * 2014-09-17 2014-12-24 上海大学 Modification method of photo-anode of dye-sensitized solar cell

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Publication number Priority date Publication date Assignee Title
CN101354971A (en) * 2008-09-12 2009-01-28 中国科学院化学研究所 Method for preparing dye sensitization TiO2 nano-crystalline film photoelectric electrode doping with metal

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Title
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103560013A (en) * 2013-11-07 2014-02-05 武汉大学 Dye-sensitized solar cell with sulfide counter electrode and preparation method thereof
CN104240957A (en) * 2014-09-17 2014-12-24 上海大学 Modification method of photo-anode of dye-sensitized solar cell

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Application publication date: 20120801