CN103065804B - A kind of preparation method of solar battery light anode - Google Patents
A kind of preparation method of solar battery light anode Download PDFInfo
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- CN103065804B CN103065804B CN201210574039.5A CN201210574039A CN103065804B CN 103065804 B CN103065804 B CN 103065804B CN 201210574039 A CN201210574039 A CN 201210574039A CN 103065804 B CN103065804 B CN 103065804B
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- Y02E10/542—Dye sensitized solar cells
Abstract
A preparation method for solar battery light anode, comprises the following steps: 1) under ultrasound condition, by TiO
2in the hydrochloric acid solution that nano-pillar is distributed to; 2) the PSS aqueous solution is joined TiO
2in nano-pillar suspension, stir; 3) the polyelectrolyte PSS do not adsorbed is removed; 4) by TiO
2nano-pillar/PSS composite construction is distributed in water, adds TiO wherein
2sol particles; 5) TiO do not adsorbed is removed
2sol particles; 6) polyelectrolyte PSS is removed; 7) by TiO
2nano-pillar/TiO
2the TiO that Nanocomposites structure disperses arrives
2in alcosol; 8) adopt knife coating slurry to be coated in the substrate of conduction abrasive particle, roasting obtains TiO
2nano-pillar/TiO
2nanocomposites light anode; 9) 24 ~ 48 are immersed in sensitising agent? h, obtains the light anode of dye sensitization.The present invention can improve photoelectric conversion efficiency.<!--1-->
Description
Technical field
The present invention relates to a kind of preparation method of solar battery light anode.
Background technology
Light anode is the important component part of DSSC, and the structure of light anode material and physics, chemical property determine the electricity conversion of DSSC to a great extent.Due to anatase TiO
2(titanium dioxide) nano particle has that larger specific area, preparation technology are simple, low cost and other advantages, is widely used smooth anode material the earliest.But the diffusion length of light induced electron in nano particle membrane electrode is shorter, the recombination probability of light induced electron is high.In recent years, research worker takes the structure of a series of stimulation optimization light anode, method uses the nano wire, nanometer rods, nanofiber etc. of one dimension as a material for light anode, because they can improve the transmission rate of light induced electron, strengthens the scattering to light.But the specific area of monodimension nanometer material general less (Rough factor is less than 200), this is unfavorable for that photocell obtains higher photoelectric current, and photovoltaic cell efficiency is generally lower.
Because zero-dimension nano particle can adsorb more dyestuff, and monodimension nanometer material accelerates the transmission rate of light induced electron, and therefore one dimension/zero-dimension nano composite construction is a kind of desirable dye-sensitized solar cell anode material.
Summary of the invention
In order to the deficiency that the photoelectric conversion efficiency of the preparation method overcoming existing solar battery light anode is lower, the invention provides a kind of preparation method improving the solar battery light anode of photoelectric conversion efficiency.
The technical solution adopted for the present invention to solve the technical problems is:
A preparation method for solar battery light anode, described preparation method comprises the following steps:
1) under ultrasound condition, by TiO
2in the hydrochloric acid solution that (titanium dioxide) nano-pillar is distributed to, form TiO
2(titanium dioxide) nano-pillar suspension, pH=2.5 ~ 4 of described hydrochloric acid solution, described TiO
2the mass volume ratio of nano-pillar and hydrochloric acid solution is 1:(100 ~ 750), unit is g/mL(grams per milliliter);
2) by PSS(polyphenyl sodium sulfonate) aqueous solution joins TiO
2in (titanium dioxide) nano-pillar suspension, PSS(polyphenyl sodium sulfonate) pH=2.5 ~ 4 of the aqueous solution, described PSS(polyphenyl sodium sulfonate) aqueous solution and TiO
2the volume ratio of (titanium dioxide) nano-pillar suspension is 1:(2 ~ 7.5); Stir, PSS(polyphenyl sodium sulfonate in whipping process) be adsorbed onto TiO
2the surface of (titanium dioxide) nano-pillar, forms TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) blank of composite construction;
3) the polyelectrolyte PSS(polyphenyl sodium sulfonate do not adsorbed is removed), obtain TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) composite construction;
4) by TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) composite construction is distributed in water, described TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) mass volume ratio of composite construction and water is 1:(50 ~ 500), unit is g/mL; Add TiO wherein
2(titanium dioxide) sol particles, described TiO
2nano-pillar/PSS(polyphenyl sodium sulfonate) composite construction and TiO
2the mass volume ratio of (titanium dioxide) sol particles is 1:(1.2 ~ 10), unit is g/mL, stirs, and obtains TiO
2(titanium dioxide) nano-pillar/PSS/TiO
2the blank of (titanium dioxide) nano particle;
5) TiO do not adsorbed is removed
2(titanium dioxide) sol particles, obtains nano-pillar/PSS(polyphenyl sodium sulfonate)/TiO
2(titanium dioxide) nano particle;
6) roasting 0.5 ~ 2h under 400 ~ 600 ° of C conditions, removes polyelectrolyte PSS(polyphenyl sodium sulfonate), obtain the TiO adsorbing frequency n=1
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure;
7) by TiO
2(titanium dioxide) nano-pillar/TiO
2the TiO that (titanium dioxide) Nanocomposites structure disperses arrives
2in (titanium dioxide) alcosol, described TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure and TiO
2the mass volume ratio of (titanium dioxide) alcosol is 1:(60 ~ 500), unit is g/mL; Stir, obtain the slurry of DSSCs light anode;
8) knife coating is adopted slurry to be coated in the substrate of conduction abrasive particle, in atmosphere after dry 20 ~ 40min, roasting 20 ~ 60min under 350 ~ 600 ° of C conditions, wherein heating rate 0.8 ~ 1.5 ° of C/min, then be cooled to room temperature; Obtain TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites light anode;
9) by TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites light anode is immersed in 24 ~ 48h in sensitising agent, obtains the light anode of dye sensitization.
Further, in described step 3), remove by centrifugal, washing, again dispersion the polyelectrolyte PSS(polyphenyl sodium sulfonate do not adsorbed).
Further again, in described step 5), remove the TiO except not adsorbing by centrifugal, washing, again dispersion
2(titanium dioxide) sol particles.
Further, in described step 8), after being cooled to room temperature, again adopt blade coating, roasting.
Beneficial effect of the present invention is mainly manifested in: can Effective Regulation TiO by changing assembling number of times
2the component of (titanium dioxide) nano-pillar and nano particle.The impact of composition on electricity conversion that have studied different nano-pillar and nano particle systematically, integrated utilization surface photovoltaic spectroscopy and electrochemical impedance spectroscopy have inquired into the factor affecting photocell conversion efficiency.
Accompanying drawing explanation
Fig. 1 is simple TiO
2(titanium dioxide) nano-pillar photocell C0 (a), TiO
2(titanium dioxide) nano-pillar/nano particle mechanical mixture photocell CM (e) and TiO
2(titanium dioxide) nano-pillar/Nanocomposites photocell C3 (b), the photoelectric current-voltage curve of C5 (c), C7 (d).
Fig. 2 is simple TiO
2(titanium dioxide) nano-pillar photocell C0 (a), TiO
2(titanium dioxide) nano-pillar/nano particle mechanical mixture photocell CM (e) and TiO
2(titanium dioxide) nano-pillar/Nanocomposites photocell C3 (b), the electrochemical impedance spectrogram of C5 (c), C7 (d).
Embodiment
Below in conjunction with accompanying drawing, the invention will be further described.
Embodiment 1
See figures.1.and.2, a kind of preparation method of solar battery light anode, described preparation method comprises the following steps:
1) under ultrasound condition, by TiO
2in the hydrochloric acid solution that (titanium dioxide) nano-pillar is distributed to, form TiO
2(titanium dioxide) nano-pillar suspension, pH=2.5 ~ 4 of described hydrochloric acid solution, described TiO
2the mass volume ratio of (titanium dioxide) nano-pillar and hydrochloric acid solution is 1:(100 ~ 750), unit is g/mL;
2) by PSS(polyphenyl sodium sulfonate) aqueous solution joins TiO
2in (titanium dioxide) nano-pillar suspension, PSS(polyphenyl sodium sulfonate) pH=2.5 ~ 4 of the aqueous solution, described PSS(polyphenyl sodium sulfonate) aqueous solution and TiO
2the volume ratio of nano-pillar suspension is 1:(2 ~ 7.5); Stir, PSS(polyphenyl sodium sulfonate in whipping process) be adsorbed onto TiO
2the surface of (titanium dioxide) nano-pillar, forms TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) blank of composite construction;
3) the polyelectrolyte PSS(polyphenyl sodium sulfonate do not adsorbed is removed), obtain TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) composite construction;
4) by TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) composite construction is distributed in water, described TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) mass volume ratio of composite construction and water is 1:(50 ~ 500), unit is g/mL; Add TiO wherein
2(titanium dioxide) sol particles, described TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) composite construction and TiO
2the mass volume ratio of (titanium dioxide) sol particles is 1:(1.2 ~ 10), unit is g/mL, stirs, and obtains TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate)/TiO
2the blank of (titanium dioxide) nano particle;
5) TiO do not adsorbed is removed
2(titanium dioxide) sol particles, obtains nano-pillar/PSS(polyphenyl sodium sulfonate)/TiO
2(titanium dioxide) nano particle;
6) roasting 0.5 ~ 2h under 400 ~ 600 ° of C conditions, removes polyelectrolyte PSS(polyphenyl sodium sulfonate), obtain the TiO adsorbing frequency n=1
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure;
7) by TiO
2(titanium dioxide) nano-pillar/TiO
2the TiO that (titanium dioxide) Nanocomposites structure disperses arrives
2in (titanium dioxide) alcosol, described TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure and TiO
2the mass volume ratio of (titanium dioxide) alcosol is 1:(60 ~ 500), unit is g/mL; Stir, obtain the slurry of DSSCs light anode;
8) knife coating is adopted slurry to be coated in the substrate of conduction abrasive particle, in atmosphere after dry 20 ~ 40min, roasting 20 ~ 60min under 305 ~ 600 ° of C conditions, wherein heating rate 0.8 ~ 1.5 ° of C/min, then be cooled to room temperature; Obtain TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites light anode;
9) by TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites light anode is immersed in 24 ~ 48h in sensitising agent, obtains the light anode of dye sensitization.
Further, in described step 3), remove by centrifugal, washing, again dispersion the polyelectrolyte PSS(polyphenyl sodium sulfonate do not adsorbed).
Further again, in described step 5), remove the TiO except not adsorbing by centrifugal, washing, again dispersion
2(titanium dioxide) sol particles.
In the present embodiment, the pH=2.5 of described hydrochloric acid solution, described TiO
2the mass volume ratio of (titanium dioxide) nano-pillar and hydrochloric acid solution is 1:100; The pH=2.5 of the PSS aqueous solution, described PSS(polyphenyl sodium sulfonate) aqueous solution and TiO
2the volume ratio of (titanium dioxide) nano-pillar suspension is 1:2; Described TiO
2nano-pillar/PSS(polyphenyl sodium sulfonate) mass volume ratio of composite construction and water is 1:50, unit is g/mL; Described TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) composite construction and TiO
2the mass volume ratio of (titanium dioxide) sol particles is 1:1.2; In step 6), roasting 0.5h under 400 ° of C conditions; Described TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure and TiO
2the mass volume ratio of (titanium dioxide) alcosol is 1:60, and unit is g/mL; In step 8), after air drying 20min, roasting 20min under 350 ° of C conditions, wherein heating rate 0.8 ° of C/min; In step 9), by TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites light anode is immersed in 24h in sensitising agent.
In the present embodiment, TiO
2(titanium dioxide) colloidal nanoparticles adopts sol-gel hydrothermal method preparation: joined by the isopropyl titanate of (50 ~ 80mL) in (20 ~ 30mL) isopropyl alcohol with vigorous stirring, then above-mentioned solution is added drop-wise in the distilled water of (300 ~ 500mL), then at 80 DEG C, stir 8h, obtain milky TiO
2(titanium dioxide) nanometer particle colloid.By the TiO obtained
2(titanium dioxide) is transferred in water heating kettle and is heated 12h at 220 DEG C, obtains the TiO of white
2(titanium dioxide) nano particle.
Porous TiO
2the preparation of (titanium dioxide) nano-pillar: be titanium source with butyl titanate take ethylene glycol as ligand solvent, adopts precursor synthesis route to prepare TiO
2(titanium dioxide) nano-pillar.Detailed process is as follows: under fast stirring, is joined in (200 ~ 250mL) ethylene glycol by (1 ~ 3mL) butyl titanate, and is incubated at 170 DEG C until solution becomes clarification.Then add (1 ~ 3mL) butyl titanate, slowly stir and be incubated 2h after white precipitate to appear.By the white precipitate absolute ethyl alcohol centrifuge washing that obtains 3 times, 100 DEG C of oven dry, obtain TiO
2(titanium dioxide) nano-pillar presoma.Then the TiO will obtained
2(titanium dioxide) nano-pillar presoma is with the programming rate of 1 DEG C/min, and roasting 2h at 300 DEG C, carries out amine process to the sample after roasting, and in the ethylenediamine of pH=10-11,90 DEG C of backflow 36h, then use deionized water centrifuge washing to pH value of solution=7.Through presoma roasting 2h at 700 DEG C of amine process, obtain the porous height degree of crystallization TiO of certain length
2(titanium dioxide) nano-pillar.
Porous TiO
2(titanium dioxide) nano-pillar/TiO
2the preparation of (titanium dioxide) sol particles complex: first, under ultrasound condition, by the TiO of (0.2 ~ 1g)
2(titanium dioxide) nano-pillar is distributed in the hydrochloric acid solution (pH=2.5 ~ 4) of (100 ~ 150mL), then by the PSS(polyphenyl sodium sulfonate of (25 ~ 50mL)) aqueous solution (pH=2.5 ~ 4) joins TiO
2in (titanium dioxide) nano-pillar suspension, vigorous mechanical agitation 30min.Because the pH value of solution is at TiO
2(pH=5.93) below the isoelectric point of (titanium dioxide), PSS(polyphenyl sodium sulfonate) surface band negative electrical charge and TiO
2nano-pillar surface band positive charge, therefore in whipping process, PSS is adsorbed onto TiO
2the surface of (titanium dioxide) nano-pillar, forms TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) composite construction.Then remove by centrifugal, washing, four repetitive processes of disperseing again the polyelectrolyte PSS(polyphenyl sodium sulfonate do not adsorbed).Then by TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) composite construction is distributed in (100 ~ 150mL) water, adds the TiO that (2 ~ 5mL) has been prepared wherein
2(titanium dioxide) sol particles, mechanical agitation 30min, obtains TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate)/TiO
2(titanium dioxide) nano particle.Adopt centrifugal, washing equally after this, the repetitive process of disperseing again removes the TiO do not adsorbed
2(titanium dioxide) sol particles, this is TiO
2(titanium dioxide) nano particle is at TiO
2an adsorption process (n=1) in (titanium dioxide) nano-pillar.Repeat above adsorption process, just can obtain the composite construction of different absorption number of times.Finally, will adsorb frequency n=3,5,7, the sample of 9, at 500 ° of C roasting 1h, removes polyelectrolyte PSS(polyphenyl sodium sulfonate), obtain the TiO of different absorption number of times
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure.
The preparation of complex light anode and the assembling of photoelectrochemistrpool pool: by the TiO of four kinds of different absorption number of times
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure (n=3,5,7,9) is distributed to the TiO of (2 ~ 3mL)
2in (titanium dioxide) alcosol, for the preparation of the slurry constructing DSSCs light anode.Knife coating is adopted to prepare light anode in TCO substrate, after obtained light anode in atmosphere dry 30min, at 450 ° of C roasting 30min(heating rates, 1 ° of C/min), after being cooled to room temperature, adopt identical method to carry out second time blade coating, roasting, finally obtain TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites light anode, is distinguished called after P3, P5, P7.Identical preparation method is adopted to construct simple TiO
2the TiO of (titanium dioxide) nano-pillar light anode and mechanical mixture
2(titanium dioxide) nano-pillar-TiO
2nano particle light anode compares, respectively called after P0 and PM.The standby light anode thickness of the ownership is 10 μm.Light anode is immersed in 24h in the N719 dyestuff of 0.5mM, obtains the light anode of dye sensitization.Adopt H
2ptCl
6pyrolysismethod prepares DSSCs to electrode, through sensitization plays light anode P0, P3, P5, P7, P9, with PM respectively with Pt to together with electrode epoxy encapsulation.Inject the electrolyte between two electrodes with capillary.The DSSCs assembled is called after C0 respectively, C3, C5, C7, C9 and CM.
Embodiment 2
In the present embodiment, in the present embodiment, the pH=3 of described hydrochloric acid solution, described TiO
2the mass volume ratio of (titanium dioxide) nano-pillar and hydrochloric acid solution is 1:500; The pH=3.5 of the PSS aqueous solution, described PSS(polyphenyl sodium sulfonate) aqueous solution and TiO
2the volume ratio of (titanium dioxide) nano-pillar suspension is 1:5; Described TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) mass volume ratio of composite construction and water is 1:200, unit is g/mL; Described TiO
2(titanium dioxide) nano-pillar/PSS composite construction and TiO
2the mass volume ratio of (titanium dioxide) sol particles is 1:5; In step 6), roasting 1h under 500 ° of C conditions; Described TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure and TiO
2the mass volume ratio of (titanium dioxide) alcosol is 1:200, and unit is g/mL; In step 8), after air drying 30min, roasting 40min under 400 ° of C conditions, wherein heating rate 1 ° of C/min; In step 9), by TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites light anode is immersed in 36h in sensitising agent.
Other schemes of the present embodiment are identical with embodiment 1.
Embodiment 3
In the present embodiment, the pH=4 of described hydrochloric acid solution, described TiO
2the mass volume ratio of (titanium dioxide) nano-pillar and hydrochloric acid solution is 1:750; PSS(polyphenyl sodium sulfonate) pH=4 of the aqueous solution, described PSS(polyphenyl sodium sulfonate) aqueous solution and TiO
2the volume ratio of (titanium dioxide) nano-pillar suspension is 1:7.5; Described TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) mass volume ratio of composite construction and water is 1:500, unit is g/mL; Described TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) composite construction and TiO
2the mass volume ratio of (titanium dioxide) sol particles is 1:10; In step 6), roasting 2h under 600 ° of C conditions; Described TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure and TiO
2the mass volume ratio of (titanium dioxide) alcosol is 1:500, and unit is g/mL; In step 8), after air drying 40min, roasting 60min under 600 ° of C conditions, wherein heating rate 1.5 ° of C/min; In step 9), by TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites light anode is immersed in 48h in sensitising agent.
Other schemes of the present embodiment are identical with embodiment 1.
Embodiment 4
See figures.1.and.2, a kind of preparation method of solar battery light anode, described preparation method comprises the following steps:
1) under ultrasound condition, by the TiO of (0.2 ~ 1g)
2(titanium dioxide) nano-pillar is distributed in the hydrochloric acid solution (pH=2.5 ~ 4) of (100 ~ 150mL).
2) by the PSS(polyphenyl sodium sulfonate of (25 ~ 50mL)) aqueous solution (pH=2.5 ~ 4) joins TiO
2in (titanium dioxide) nano-pillar suspension, vigorous mechanical agitation 30min.PSS(polyphenyl sodium sulfonate in whipping process) be adsorbed onto TiO
2the surface of (titanium dioxide) nano-pillar, forms TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) composite construction.
3) remove by centrifugal, washing, four repetitive processes of disperseing again the polyelectrolyte PSS(polyphenyl sodium sulfonate do not adsorbed).
4) by TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate) composite construction is distributed in (100 ~ 150mL) water, adds the TiO that (2 ~ 3mL) has been prepared wherein
2(titanium dioxide) sol particles, mechanical agitation 30min, obtains TiO
2(titanium dioxide) nano-pillar/PSS(polyphenyl sodium sulfonate)/TiO
2(titanium dioxide) nano particle.
5) adopt centrifugal, washing, the repetitive process of disperseing again removes the TiO do not adsorbed
2sol particles, this is TiO
2(titanium dioxide) nano particle is at TiO
2an adsorption process (n=1) in (titanium dioxide) nano-pillar.
6) at 500 ° of C roasting 1h, polyelectrolyte PSS(polyphenyl sodium sulfonate is removed), obtain the TiO adsorbing frequency n=1
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure.
7) by TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure (n=1) is distributed to the TiO of (2 ~ 3mL)
2in (titanium dioxide) alcosol, for the preparation of the slurry constructing DSSCs light anode.
8) knife coating is adopted at TCO(transparent conductive oxide coated glass) light anode is prepared in substrate, after obtained light anode in atmosphere dry 30min, at 450 ° of C roasting 30min(heating rates, 1 ° of C/min), after being cooled to room temperature, adopt identical method to carry out second time blade coating, roasting, finally obtain TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites light anode, is distinguished called after P1.
9) light anode is immersed in 24h in the N719 dyestuff of 0.5mM, obtains the light anode of dye sensitization.
10) H is adopted
2ptCl
6pyrolysismethod prepares the Pt of DSSCs to electrode, and with preparation light anode assembling battery.Test performance.
Embodiment 5
Other are with embodiment 4, unlike the TiO of preparation absorption frequency n=3
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure.
Embodiment 6
Other are with embodiment 4, unlike the TiO of preparation absorption frequency n=5
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure.
Embodiment 7
Other are with embodiment 4, unlike the TiO of preparation absorption frequency n=7
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure.
Embodiment 8
Other are with embodiment 4, unlike the TiO of preparation absorption frequency n=9
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites structure.
Embodiment 9
Other are with embodiment 4, preparation TiO
2(titanium dioxide) nano-pillar/TiO
2the composite construction of (titanium dioxide) nano particle mechanical mixture, for contrast test.
Test result:
Fig. 1 is TiO
2photronic photoelectric current-photovoltage curve prepared by (titanium dioxide) complex light anode.Corresponding photocell Argument List in Table 1.
Note: J
sc: short-circuit photocurrent.V
oc: open-circuit photovoltage.FF: fill factor, curve factor.η: photoelectric conversion efficiency.
Table 1
Incident intensity P used herein
infor 40mWcm
2, the test value of battery performance is at least the mean value of three sample test values.Can see, photronic photoelectric conversion efficiency is increasing from n=0 gradually to 5, then successively decreases.Based on TiO
2the C3 that (titanium dioxide) nano-pillar/Nanocomposites light anode is constructed, the photoelectric conversion efficiency of C5 and C7 is 7.51,8.06 and 7.42% respectively, than the TiO of mechanical mixture
2the photoelectric efficiency 6.93% of the CM that (titanium dioxide) nano-pillar-nano particle light anode is constructed is high.Show: the frequency n of sorption cycle plays very important effect for the photoelectric conversion efficiency of DSSCs, select suitable cycle-index n effectively can improve the photoelectric properties of DSSCs, by the further optimization process to light anode, electricity conversion is expected to further be improved.
Fig. 2 is at 10mWcm
-2tiO simple under illumination
2(titanium dioxide) nano-pillar photocell C0 (a) and TiO
2(titanium dioxide) nano-pillar/TiO
2(titanium dioxide) Nanocomposites photocell C3 (b), the electrochemical impedance spectrogram of C5 (c), C7 (d).As a rule, at 100mWcm
-2this Tequ line of the energy obtained under light intensity can demonstrate three semicircles, respectively corresponding three frequency ranges.But in the experimentation of reality, we only observed the semicircle of intermediate frequency zone and high frequency region, correspond respectively to dye sensitization light anode | I
3 -/ I
-electrolyte interface and Pt|I
3 -/ I
-electrolyte interface.This is because beam intensity ratio is more weak, and the semicircle of low frequency range has been dissolved in the semicircle of intermediate frequency zone.Data shown in table 2 are conducive to understanding and explaining the interfacial reaction occurred in DSSCs.
Table 2
Wherein, R and C represents resistance and electric capacity respectively.R
1be series resistance, represent the transmission resistance of two FTO electrodes.If TiO
2the thickness of film is designated as L, so R
ct(=r
ct/ L) just represent TiO
2i in complex light anode and electrolyte
3 -between transferring charge resistance.C
1(=c
1l) be TiO
2the chemical electric capacity of complex light anode.Z
difrepresent and I in electrolyte
3 -this spy can spread relevant Warburg resistance, see following formula
Z
dif=R
dif{ tanh (j ω τ) 1/2/ (j ω τ) 1/2} wherein, R
dif=B/Y
o1, τ=B
2, B is parameter.R
2and C
2the transferring charge resistance to electrode and double layer capacity respectively.R
ctvalue is a key parameter, which determines the speed of DSSCs median surface electron transfer rate.Clearly, the R of C0, C3, C5, C7
ct16.9,1.72,0.20 respectively, and 1.75 Ω, namely interface resistance is less, and interface electric transmission is faster, and electricity conversion η is higher.Wherein the transferring charge of n=5 is the fastest, also has the highest electricity conversion.
Claims (5)
1. a preparation method for solar battery light anode, is characterized in that: described preparation method comprises the following steps:
1) under ultrasound condition, by TiO
2in the hydrochloric acid solution that nano-pillar is distributed to, form TiO
2nano-pillar suspension, pH=2.5 ~ 4 of described hydrochloric acid solution, described TiO
2the mass volume ratio of nano-pillar and hydrochloric acid solution is 1:(100 ~ 750), unit is g/ml;
2) the PSS aqueous solution is joined TiO
2in nano-pillar suspension, pH=2.5 ~ 4 of the PSS aqueous solution, the described PSS aqueous solution and TiO
2the volume ratio of nano-pillar suspension is 1:(2 ~ 7.5); Stir, in whipping process, PSS is adsorbed onto TiO
2the surface of nano-pillar, forms TiO
2the blank of nano-pillar/PSS composite construction;
3) remove the polyelectrolyte PSS do not adsorbed, obtain TiO
2nano-pillar/PSS composite construction;
4) by TiO
2nano-pillar/PSS composite construction is distributed in water, described TiO
2the mass volume ratio of nano-pillar/PSS composite construction and water is 1:(50 ~ 500), unit is g/ml; Add TiO wherein
2sol particles, described TiO
2nano-pillar/PSS composite construction and TiO
2the mass volume ratio of sol particles is 1:(1.2 ~ 10), unit is g/ml, stirs, and obtains TiO
2nano-pillar/PSS/TiO
2the blank of nano particle;
5) TiO do not adsorbed is removed
2sol particles, obtains nano-pillar/PSS/TiO
2nano particle;
6) roasting 0.5 ~ 2h under 400 ~ 600 DEG C of conditions, removes polyelectrolyte PSS, obtains the TiO adsorbing frequency n=1
2nano-pillar/TiO
2nanocomposites structure;
7) by TiO
2nano-pillar/TiO
2the TiO that Nanocomposites structure disperses arrives
2in alcosol, described TiO
2nano-pillar/TiO
2nanocomposites structure and TiO
2the mass volume ratio of alcosol is 1:(60 ~ 500), unit is g/ml; Stir, obtain the slurry of DSSCs light anode;
8) knife coating is adopted slurry to be coated in the substrate of conduction abrasive particle, in atmosphere after dry 20 ~ 40min, roasting 20 ~ 60min under 350 ~ 600 DEG C of conditions, wherein heating rate 0.8 ~ 1.5 DEG C/min, then be cooled to room temperature; Obtain TiO
2nano-pillar/TiO
2nanocomposites light anode;
9) by TiO
2nano-pillar/TiO
2nanocomposites light anode is immersed in 24 ~ 48h in sensitising agent, obtains the light anode of dye sensitization.
2. the preparation method of a kind of solar battery light anode as claimed in claim 1, is characterized in that: described step 3) in, remove by centrifugal, washing, again dispersion the polyelectrolyte PSS do not adsorbed.
3. the preparation method of a kind of solar battery light anode as claimed in claim 1, is characterized in that: described step 5) in, remove by centrifugal, washing, again dispersion the TiO do not adsorbed
2sol particles.
4. the preparation method of a kind of solar battery light anode as described in one of claims 1 to 3, is characterized in that: described step 8) in, after being cooled to room temperature, again adopt blade coating, roasting.
5. the preparation method of a kind of solar battery light anode as described in one of claims 1 to 3, it is characterized in that: described sensitising agent is N719 ruthenium dye, i.e. two-tetrabutylammonium-bis-(isothiocyano) two (2,2'-bipyridine-4,4'-dicarboxyl) ruthenium (II).
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