CN105321721A - Preparation method of dye sensitization solar cell photo-anode material - Google Patents
Preparation method of dye sensitization solar cell photo-anode material Download PDFInfo
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- CN105321721A CN105321721A CN201510870776.3A CN201510870776A CN105321721A CN 105321721 A CN105321721 A CN 105321721A CN 201510870776 A CN201510870776 A CN 201510870776A CN 105321721 A CN105321721 A CN 105321721A
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- titanium dioxide
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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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- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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Abstract
The invention relates to a preparation method of a dye sensitization solar cell photo-anode material, which belongs to the fields of a functional material and a novel composite material, and particularly relates to a nickel oxide particle/titanium dioxide nano-rod composite material. The nickel oxide particle/titanium dioxide nano-rod composite material has a large specific surface area and good light scattering effect; and meanwhile, a PN-junction structure formed by the nickel oxide particle/titanium dioxide nano-rod composite material can accelerate rapid transmission of electrons, therefore, when the nickel oxide particle/titanium dioxide nano-rod composite material is used for a dye sensitization solar cell, the photoelectric performance is good. Meanwhile, the preparation method is simple and has a practical prospect.
Description
Technical field
The invention belongs to functional material and advanced composite material (ACM) field, particularly the preparation method of a kind of nickel oxide particle/titanium dioxide nano-rod composite material.
Background technology
In recent years, DSSC (DSSCs) is paid close attention to widely because the features such as its low cost, easily assembling receive.The core of DSSCs is nano crystal semiconductor optical anode, and it is usually by nano-TiO
2porous membrane is formed, and is the most important part of solar cell.Light anode plays an important role to solar cell photoelectric performance: as provided the path of electric transmission, absorbing dye and ensure sufficient liquid channel etc.
Research finds that the photoelectric properties of restriction DSSC mainly contain the factor of two aspects: being the absorption of battery thin film to sunlight on the one hand, is the transmission of electronics in titanium dioxide semiconductor film on the other hand.The performance of titanium dioxide semiconductor light anode seriously governs the photoelectric conversion efficiency of battery.As the important component part of light anode, the pattern of titanic oxide material and the structures shape electric transmission dynamic performance of light anode.Particularly titanium dioxide has more fault of construction, causes that the transmission time of electronics in photo-anode film is long, electron lifetime is short.
In numerous pattern, titanium dioxide nano-rod or this material of nano wire have one dimension cylindrical geometry body configuration, can provide transmitting electric field, make electronic remote from the surface of nanometer rods or nano wire, reduce electric surface density, increase effective separation of charge.The more important thing is, light induced electron effectively can reduce crystal boundary along the transmission of one dimension long axis direction and catch photoelectronic, accelerates the transmission rate of electronics, weakens the compound of light induced electron, contributes to the photoelectric conversion efficiency improving DSSC.But nanometer rods light anode material also exists very important problem: specific area is too little, light scattering effect is poor, cause the short circuit current of battery too low.
Summary of the invention
Technical problem to be solved by this invention is: nanometer rods light anode material specific area is too little, and for solving this technical problem, the technical solution used in the present invention is:
Provide the preparation method of a kind of nickel oxide particle/titanium dioxide nano-rod composite material:
(1) titania powder be alkali lye and the quality of 1 ~ 15M by concentration being 1 ~ 5g mixes, and stir, ultrasonic half an hour;
(2) mixed system obtained in step (1) is transferred in the reactor of 100ml, 160 DEG C ~ 200 DEG C hydro-thermal reactions 12 ~ 60 hours;
(3) by centrifugal for step (2) reacted system, and respectively with dilute hydrochloric acid solution, distilled water washing, the product obtained dries 24h at 60 DEG C, obtains proton titanate nanometer rods,
Wherein, centrifuge speed is 6000rpm/min, and the concentration of watery hydrochloric acid is 0.1mol.L
-1, wash 2 times, distilled water washs 3 times;
(4) the proton titanate nanometer rods of preparation in 0.1 ~ 0.5g step (3) is added the NiCl that volume is 10 ~ 100ml
2stir after 10 minutes in solution, adding urea adjust ph is 10, and then 80 DEG C of water-baths cool after 2 ~ 10 hours naturally,
Wherein, NiCl
2niCl in solution
2for 10mmol;
(5) by centrifugal for step (4) reacted system, and respectively with deionized water, absolute ethanol washing to pH value be 7,60 DEG C dry after, in air 500 degree sinter 2h, obtain nickel oxide particle/titanium dioxide nano-rod composite material,
Wherein, centrifuge speed is 6000rpm/min, and washing precipitate 3 times and 1 time distinguished by use deionized water and absolute ethyl alcohol successively.
DSSC prepared by the present invention, for light anode semi-conducting material with nickel oxide particle/titanium dioxide nano-rod composite material, N719 dyestuff is photosensitizer, and platinum electrode is to electrode, forms DSSC with liquid iodine electrolyte.
The invention has the beneficial effects as follows the nickel oxide particle/titanium dioxide nano-rod composite material by adopting described preparation method to obtain, effectively improve specific area and the light scattering effect of light anode, large specific area can adsorb more dye molecule, increase the short circuit current of respective battery, and then improve the photoelectric conversion efficiency of battery, the P-N junction structure that simultaneous oxidation nickel and titanium dioxide surface are formed effectively can be separated light induced electron and promote the transmission of electronics, electron recombination probability reduces greatly, the collection efficiency of electronics is improved, the performance of respective battery have also been obtained great raising.With nickel oxide particle of the present invention/titanium dioxide nano-rod composite material for battery light anode material, the DSSC be assembled into, has the advantages such as with low cost, photoelectric conversion efficiency is high, preparation technology is simple.
Accompanying drawing explanation
Photoelectric current-the voltage curve of the solar cell that Fig. 1 is light anode material with nickel oxide particle/titanium dioxide nano-rod composite material;
The AC impedance curve that Fig. 2 is the solar cell of light anode material with nickel oxide particle/titanium dioxide nano-rod composite material.
Embodiment
Embodiment 1:
(1) titania powder be alkali lye and the quality of 10M by concentration being 3g mixes, and stir, ultrasonic half an hour;
(2) system obtained in step (1) is transferred in the reactor of 100ml, 180 DEG C of hydro-thermal reactions 48 hours;
(3) step (2) reacted system is carried out when rotating speed is 6000rpm/min centrifugal, and use 0.1mol.L respectively
-1dilute hydrochloric acid solution, distilled water and ethanol respectively wash 2 times, 3 times and 1 time, the product obtained dries 24h at 60 DEG C, obtains proton titanate nanometer rods,
The specific area that BET detects above-mentioned proton titanate nanometer rods is 18m
2/ g;
(4) the proton titanate nanometer rods of preparation in 0.5g step (3) is added volume be 50ml containing 10mmolNiCl
2solution in stir after 10 minutes, adding urea adjust ph is 10, then 80 DEG C of water-baths coolings naturally after 6 hours;
(5) step (4) reacted system is carried out centrifugal when rotating speed is 6000rpm/min, and be 7 by deionized water, absolute ethanol washing to pH value respectively, after 60 DEG C of oven dry, in air, 500 degree of sintering 2h, obtain nickel oxide particle/titanium dioxide nano-rod composite material.
The specific area that BET detects above-mentioned nickel oxide particle/titanium dioxide nano-rod composite material is 82m
2/ g.
(6) nickel oxide particle of above-mentioned for 0.5g preparation/titanium dioxide nano-rod composite material and 0.5ml absolute ethyl alcohol are added in mortar, grind to form starchiness, with glass bar, it is coated on electro-conductive glass equably.After drying, at 450 DEG C of temperature, sinter 0.5h, then in N-719 dye solution, soak 24h, make light anode;
(7) be to electrode with Pt electrode, be assembled into solar cell.Electrolyte is for containing 0.5MLiI, 0.05MI
2with the acetonitrile solution of 0.5MTBP (4-tert-butylpyridine), the Validity Test area detecting battery is 0.25cm
2.
With solar simulator (xenon lamp, AM1.5,100mW/cm
2) and CIMPS-2 electrochemical workstation measure the photovoltaic performance of battery.As shown in figure 1 and table 1, the short circuit current of nickel oxide particle/titanium dioxide nano-rod composite material battery is apparently higher than the short circuit current of nanometer rods, by calculating the photoelectric conversion efficiency of battery, the conversion efficiency of nickel oxide particle/titanium dioxide nano-rod composite material battery is 1.13%, apparently higher than 0.28% of nanometer rods battery.
With solar simulator (xenon lamp, AM1.5,100mW/cm
2) and CIMPS-2 electrochemical workstation measure the AC impedance performance of battery, as shown in Figure 2.Sample spectral line is made up of a typical semicircle, be assigned as the transfer resistance of electric charge, half circular diameter shows that more greatly charge transfer resistance is larger, this shows, the resistance of composite material battery is less than nanometer rods, show that electronics transmits at composite material the resistance be subject to and is less than nanometer rods, the transmission of pn junction structure to electronics of composite material plays impetus.
Adopt CIMPS-2 electrochemical workstation, the blue LED that the wavelength that light source is driven by PP210 is 470nm provides, and measures Intensity Modulated Photocurrent Spectroscopy (IMPS) and the intensity modulated photovoltaic spectrum (IMVS) of battery.Result of calculation is as shown in table 2, as can be seen from the table the electric transmission time (τ of composite material
d) obviously shorten, electron lifetime increases (τ
n), show that composite material has good electric transmission dynamic performance, the pn junction structure of composite material serves the effect of improvement to electric transmission dynamic performance.
Experimentally result, the nickel oxide particle adopting preparation method of the present invention to prepare/titanium dioxide nano-rod composite material, had sizable raising than the performance of single nanometer rods, by means of the pn junction structure of composite material, electric transmission dynamic performance be improved significantly.As shown in the figure, Fig. 1 is the I-V curve of original nanometer rods and the I-V curve of nickel oxide particle of the present invention/titanium dioxide nano-rod composite material; Table 1 is according to I-V curve calculation performance parameter out; Fig. 2 is the AC impedance curve of original nanometer rods and nickel oxide particle of the present invention/titanium dioxide nano-rod composite material; Table 2 is the performance parameters calculated according to IMPS and IMVS.
Table 1
| J sc(mA/cm 2) | V oc(V) | FF | η(℅) | |
| Nanometer rods | 0.90 | 0.605 | 0.52 | 0.28 |
| Composite material | 3.28 | 0.780 | 0.44 | 1.13 |
Table 2
| τ d(ms) | τ n(ms) | |
| Nanometer rods | 1.46 | 54 |
| Composite material | 1.18 | 79.6 |
Claims (8)
1. a preparation method for nickel oxide particle/titanium dioxide nano-rod composite material, is characterized in that: described preparation method is,
(1) titania powder be alkali lye and the quality of 1 ~ 15M by concentration being 1 ~ 5g mixes, and stir, ultrasonic half an hour;
(2) system obtained in step (1) is transferred in the reactor of 100ml, 160 DEG C ~ 200 DEG C hydro-thermal reactions 12 ~ 60 hours;
(3) by centrifugal for step (2) reacted system, and respectively with dilute hydrochloric acid solution, distilled water washing, the product obtained dries 24h at 60 DEG C, obtains proton titanate nanometer rods;
(4) the proton titanate nanometer rods of preparation in 0.1 ~ 0.5g step (3) is added the NiCl that volume is 10 ~ 100ml
2stir after 10 minutes in solution, adding urea adjust ph is 10, and then 80 DEG C of water-baths cool after 2 ~ 10 hours naturally;
(5) by centrifugal for step (4) reacted system, and respectively with deionized water, absolute ethanol washing to pH value be 7,60 DEG C dry after, in air 500 degree sinter 2h, obtain nickel oxide particle/titanium dioxide nano-rod composite material.
2. the preparation method of nickel oxide particle/titanium dioxide nano-rod composite material as claimed in claim 1, it is characterized in that: in step (3), time centrifugal, rotating speed is 6000rpm/min.
3. the preparation method of nickel oxide particle/titanium dioxide nano-rod composite material as claimed in claim 1, it is characterized in that: in step (3), the concentration of watery hydrochloric acid is 0.1mol.L
-1.
4. the preparation method of nickel oxide particle/titanium dioxide nano-rod composite material as claimed in claim 1, is characterized in that: in step (3), watery hydrochloric acid washs 2 times, and distilled water washs 3 times.
5. the preparation method of nickel oxide particle/titanium dioxide nano-rod composite material as claimed in claim 1, is characterized in that: in step (4), NiCl
2niCl in solution
2for 10mmol.
6. the preparation method of nickel oxide particle/titanium dioxide nano-rod composite material as claimed in claim 1, it is characterized in that: in step (5), time centrifugal, rotating speed is 6000rpm/min.
7. the preparation method of nickel oxide particle/titanium dioxide nano-rod composite material as claimed in claim 1, is characterized in that: in step (5), and washing precipitate 3 times and 1 time distinguished by deionized water and absolute ethyl alcohol.
8. the application of nickel oxide particle/titanium dioxide nano-rod composite material as claimed in claim 1, it is characterized in that: described is applied as, with described nickel oxide particle/titanium dioxide nano-rod composite material for light anode semi-conducting material, N719 dyestuff is photosensitizer, platinum electrode is to electrode, forms DSSC with liquid iodine electrolyte.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108551298A (en) * | 2018-05-23 | 2018-09-18 | 深圳市创艺工业技术有限公司 | A kind of environment-protecting intelligent apparatus for building |
| CN108962626A (en) * | 2018-08-14 | 2018-12-07 | 东北大学 | A kind of composite material with pn-junction structure for supercapacitor, electrode material for super capacitor and preparation method thereof |
| CN109003821A (en) * | 2018-08-14 | 2018-12-14 | 东北大学 | A kind of ultra-high dielectric coefficient composite material, preparation method and application |
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| CN101866753A (en) * | 2009-04-16 | 2010-10-20 | 中国科学院物理研究所 | Photoanode surface treatment method of dye sensitization solar batteries |
| CN103833076A (en) * | 2012-11-27 | 2014-06-04 | 王泰林 | Nickel oxide-titanium dioxide nano composite material |
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| CN101866753A (en) * | 2009-04-16 | 2010-10-20 | 中国科学院物理研究所 | Photoanode surface treatment method of dye sensitization solar batteries |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108551298A (en) * | 2018-05-23 | 2018-09-18 | 深圳市创艺工业技术有限公司 | A kind of environment-protecting intelligent apparatus for building |
| CN108962626A (en) * | 2018-08-14 | 2018-12-07 | 东北大学 | A kind of composite material with pn-junction structure for supercapacitor, electrode material for super capacitor and preparation method thereof |
| CN109003821A (en) * | 2018-08-14 | 2018-12-14 | 东北大学 | A kind of ultra-high dielectric coefficient composite material, preparation method and application |
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Inventor after: Qu Jie Inventor after: Lv Zhigang Inventor after: Ren Yurong Inventor after: Yuan Ningyi Inventor after: Ding Jianning Inventor before: Qu Jie Inventor before: Yuan Ningyi Inventor before: Ding Jianning |
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