CN105321721B - A kind of preparation method of dye-sensitized solar cell anode material - Google Patents
A kind of preparation method of dye-sensitized solar cell anode material Download PDFInfo
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- CN105321721B CN105321721B CN201510870776.3A CN201510870776A CN105321721B CN 105321721 B CN105321721 B CN 105321721B CN 201510870776 A CN201510870776 A CN 201510870776A CN 105321721 B CN105321721 B CN 105321721B
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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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- 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
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Abstract
A kind of preparation method of dye-sensitized solar cell anode material, the invention belongs to functional material and advanced composite material (ACM) field, specially nickel oxide particle/titanium dioxide nano-rod composite.The nickel oxide particle/titanium dioxide nano-rod composite has larger specific surface area, good light scattering effect, PN junction structure constructed by simultaneous oxidation nickel particle/titanium dioxide nano-rod composite can accelerate the quick transmission of electronics, therefore the nickel oxide particle in the present invention/titanium dioxide nano-rod composite is used to present good photoelectric properties during DSSC.Its preparation method is easy simultaneously, has practical prospect.
Description
Technical field
The invention belongs to functional material and advanced composite material (ACM) field, more particularly to a kind of nickel oxide particle/titanium dioxide
The preparation method of nanometer rod composite material.
Background technology
In recent years, DSSC (DSSCs) due to its low cost, be easily assembled the features such as receive it is extensive
Concern.DSSCs core is nano crystal semiconductor optical anode, and it is generally by nano-TiO2Porous membrane is formed, and is the sun
Can the most important part of battery.Light anode plays an important role to solar cell photoelectric performance：The road of electric transmission is such as provided
Footpath, adsorb dyestuff and ensure sufficient liquid channel etc..
Research finds that the photoelectric properties for restricting DSSC mainly have both sides factor：On the one hand it is electricity
Absorption of the pond film to sunshine, on the other hand it is transmission of the electronics in titanium dioxide semiconductor film.Titanium dioxide is partly led
The performance of body light anode seriously governs the photoelectric transformation efficiency of battery.As the important component of light anode, titanium dioxide
The pattern of material and structures shape the electric transmission dynamic performance of light anode.Particularly titanium dioxide has more structure
Defect, causes that transmission time of the electronics in photo-anode film is long, electron lifetime is short.
In numerous patterns, titanium dioxide nano-rod or this material of nano wire have one-dimensional cylindrical geometry body configuration, energy
It is enough that transmitting electric field is provided, make surface of the electronics away from nanometer rods or nano wire, reduce electric surface density, increase effective electric charge
Separation.Caught importantly, transmission of the light induced electron along one-dimensional long axis direction can efficiently reduce crystal boundary to photoelectronic
Obtain, accelerate the transmission rate of electronics, weaken the compound of light induced electron, the photoelectricity for being favorably improved DSSC turns
Change efficiency.But nanometer rods light anode material there is it is very important the problem of：Specific surface area is too small, light scattering effect is poor, causes
The short circuit current of battery is too low.
The content of the invention
The technical problems to be solved by the invention are：Nanometer rods light anode material specific surface area is too small, to solve this
Technical problem, the technical solution adopted by the present invention are：
Provide a kind of preparation method of nickel oxide particle/titanium dioxide nano-rod composite：
(1) alkali lye that concentration is 1~15M is mixed with the titania powder that quality is 1~5g, and stirred, ultrasound half
Hour；
(2) mixed system obtained in step (1) is transferred in 100ml reactor, 160 DEG C~200 DEG C hydro-thermals are anti-
Answer 12~60 hours；
(3) the reacted system of step (2) is centrifuged, and respectively with dilute hydrochloric acid solution, distillation water washing, obtained product
24h is dried at 60 DEG C, obtains proton titanate nanometer rods,
Wherein, centrifuge speed 6000rpm/min, the concentration of watery hydrochloric acid is 0.1mol.L-1, wash 2 times, distillation washing
Wash 3 times；
(4) it is 10~100ml's the proton titanate nanometer rods prepared in 0.1~0.5g steps (3) to be added into volume
NiCl2After being stirred 10 minutes in solution, it is 10 to add urea regulation pH value, then after 2~10 hours of 80 DEG C of water-baths certainly
So cooling,
Wherein；NiCl2NiCl in solution2For 10mmol；
(5) the reacted system of step (4) is centrifuged, and it is 7 to be washed respectively with deionized water, absolute ethyl alcohol to pH value,
After 60 DEG C of drying, 500 degree of sintering 2h, obtain nickel oxide particle/titanium dioxide nano-rod composite in air,
Wherein, centrifuge speed 6000rpm/min, washing precipitate 3 is distinguished with deionized water and absolute ethyl alcohol successively
It is secondary and 1 time.
DSSC prepared by the present invention, it is with nickel oxide particle/titanium dioxide nano-rod composite wood
Expect that for light anode semi-conducting material, N719 dyestuffs be photosensitizer, platinum electrode is to electrode, and dyestuff is formed with liquid iodine electrolyte
Sensitization solar battery.
The beneficial effects of the invention are as follows the nickel oxide particle/titanium dioxide nano-rod obtained by using the preparation method
Composite, is effectively improved the specific surface area and light scattering effect of light anode, and big specific surface area can be adsorbed more
Dye molecule, increase the short circuit current of respective battery, and then improve the photoelectric transformation efficiency of battery, simultaneous oxidation nickel and titanium dioxide
The P-N junction structure that titanium surface is formed can efficiently separate light induced electron and promote the transmission of electronics, and electronics recombination probability is significantly
Reduce, the collection efficiency of electronics is improved, and the performance of respective battery is also greatly improved.With oxygen of the present invention
Change nickel particle/titanium dioxide nano-rod composite is battery light anode material, the DSSC being assembled into, is had
Have the advantages that cost is cheap, photoelectric transformation efficiency is high, preparation technology is simple.
Brief description of the drawings
Photoelectricity of the Fig. 1 using nickel oxide particle/titanium dioxide nano-rod composite as the solar cell of light anode material
Stream-voltage curve；
Exchanges of the Fig. 2 using nickel oxide particle/titanium dioxide nano-rod composite as the solar cell of light anode material
Impedance curve.
Embodiment
Embodiment 1：
(1) alkali lye that concentration is 10M is mixed with the titania powder that quality is 3g, and stirred, ultrasonic half an hour；
(2) system obtained in step (1) is transferred in 100ml reactor, 180 DEG C of hydro-thermal reactions 48 hours；
(3) step (2) reacted system is centrifuged in the case where rotating speed is 6000rpm/min, and used respectively
0.1mol.L-1Dilute hydrochloric acid solution, respectively washing 2 times, 3 times and 1 time of distilled water and ethanol, obtained product is dried at 60 DEG C
24h, proton titanate nanometer rods are obtained,
The specific surface area that BET detects above-mentioned proton titanate nanometer rods is 18m2/g；
(4) the proton titanate nanometer rods prepared in 0.5g steps (3) are added into volume and contains 10mmol for 50ml
NiCl2Solution in stir 10 minutes after, add urea regulation pH value be 10, then 80 DEG C of water-baths are naturally cold after 6 hours
But；
(5) step (4) reacted system is centrifuged in the case where rotating speed is 6000rpm/min, and used respectively
Deionized water, absolute ethyl alcohol wash to pH value be 7,60 DEG C drying after, in air 500 degree sinter 2h, obtain nickel oxide particle/bis-
TiOx nano rod composite material.
The specific surface area that BET detects above-mentioned nickel oxide particle/titanium dioxide nano-rod composite is 82m2/g。
(6) nickel oxide particle of the above-mentioned preparations of 0.5g/titanium dioxide nano-rod composite is added with 0.5ml absolute ethyl alcohols
It is added in mortar, is ground into starchiness, is equably coated in it on electro-conductive glass with glass bar.After drying, at a temperature of 450 DEG C
0.5h is sintered, then 24h is soaked in N-719 dye solutions, light anode is made；
(7) using Pt electrodes as to electrode, it is assembled into solar cell.Electrolyte is LiI containing 0.5M, 0.05M I2With
0.5M TBP (4-tert-butylpyridine) acetonitrile solution, the Validity Test area for detecting battery are 0.25cm2。
With solar simulator (xenon lamp, AM 1.5,100mW/cm2) and CIMPS-2 electrochemical workstations measurement battery light
Lie prostrate performance.As shown in figure 1 and table 1, the short circuit current of nickel oxide particle/titanium dioxide nano-rod composite battery apparently higher than
The short circuit current of nanometer rods, by the way that the photoelectric transformation efficiency of battery is calculated, nickel oxide particle/titanium dioxide nano-rod is compound
The conversion efficiency of material cell is 1.13%, hence it is evident that higher than the 0.28% of nanometer rods battery.
With solar simulator (xenon lamp, AM 1.5,100mW/cm2) and CIMPS-2 electrochemical workstations measurement battery friendship
Flow resistance anti-performance, as shown in Figure 2.Sample spectral line is made up of a typical semicircle, is assigned as the transfer resistance of electric charge, semicircle
Diameter shows that more greatly charge transfer resistance is bigger, it can thus be seen that the resistance of composite battery is less than nanometer rods, shows electricity
Son is less than nanometer rods in the resistance that is subject to of composite transmission, and the transmission of the pn-junction structure of composite to electronics has played promotion work
With.
Using CIMPS-2 electrochemical workstations, the wavelength that light source is driven by PP210 is 470nm blue LED
There is provided, determine the Intensity Modulated Photocurrent Spectroscopy (IMPS) and intensity modulated photovoltaic spectrum (IMVS) of battery.The result of calculation such as institute of table 2
Show, as can be seen from the table the electric transmission time (τ of composited) substantially shorten, electron lifetime increases (τn), show compound
Material has good electric transmission dynamic performance, and the pn-junction structure of composite serves to electric transmission dynamic performance
Improved effect.
According to experimental result, the nickel oxide particle/titanium dioxide nano-rod prepared using preparation method of the present invention
Composite, there is sizable raising than the performance of single nanometer rods, by means of the pn-junction structure of composite, electronics passes
Defeated dynamic performance be improved significantly.As illustrated, Fig. 1 is the I-V curve of original nanometer rods and oxygen of the present invention
Change the I-V curve of nickel particle/titanium dioxide nano-rod composite；Table 1 is the performance parameter calculated according to I-V curve；
Fig. 2 is the AC impedance song of original nanometer rods and nickel oxide particle of the present invention/titanium dioxide nano-rod composite
Line；Table 2 is the performance parameter calculated according to IMPS and IMVS.
Table 1
| Jsc(mA/cm2) | Voc(V) | FF | η(℅) | |
| Nanometer rods | 0.90 | 0.605 | 0.52 | 0.28 |
| Composite | 3.28 | 0.780 | 0.44 | 1.13 |
Table 2
| τd(ms) | τn(ms) | |
| Nanometer rods | 1.46 | 54 |
| Composite | 1.18 | 79.6 |
Claims (7)
- A kind of 1. application of nickel oxide particle/titanium dioxide nano-rod composite, it is characterised in that：Described application is, with Described nickel oxide particle/titanium dioxide nano-rod composite is light anode semi-conducting material, and N719 dyestuffs are photosensitizer, Platinum electrode is to electrode, and DSSC is formed with liquid iodine electrolyte；The preparation method of described nickel oxide particle/titanium dioxide nano-rod composite is,(1) alkali lye that concentration is 1~15M is mixed with the titania powder that quality is 1~5g, and stirred, ultrasonic half an hour；(2) system obtained in step (1) is transferred in 100ml reactor, 160 DEG C~200 DEG C hydro-thermal reactions 12~60 Hour；(3) the reacted system of step (2) is centrifuged, and respectively with dilute hydrochloric acid solution, distillation water washing, obtained product is 60 24h is dried at DEG C, obtains proton titanate nanometer rods；(4) the proton titanate nanometer rods prepared in 0.1~0.5g steps (3) are added into the NiCl that volume is 10~100ml2It is molten After being stirred 10 minutes in liquid, it is 10 to add urea regulation pH value, then natural cooling after 2~10 hours of 80 DEG C of water-baths；(5) the reacted system of step (4) is centrifuged, and it is 7,60 DEG C to be washed respectively with deionized water, absolute ethyl alcohol to pH value After drying, 500 degree of sintering 2h, obtain nickel oxide particle/titanium dioxide nano-rod composite in air.
- 2. the application of nickel oxide particle as claimed in claim 1/titanium dioxide nano-rod composite, it is characterised in that：Step Suddenly in (3), rotating speed is 6000rpm/min during centrifugation.
- 3. the application of nickel oxide particle as claimed in claim 1/titanium dioxide nano-rod composite, it is characterised in that：Step Suddenly in (3), the concentration of watery hydrochloric acid is 0.1mol.L-1。
- 4. the application of nickel oxide particle as claimed in claim 1/titanium dioxide nano-rod composite, it is characterised in that：Step Suddenly in (3), watery hydrochloric acid washs 2 times, distillation water washing 3 times.
- 5. the application of nickel oxide particle as claimed in claim 1/titanium dioxide nano-rod composite, it is characterised in that：Step Suddenly in (4), NiCl2NiCl in solution2For 10mmol.
- 6. the application of nickel oxide particle as claimed in claim 1/titanium dioxide nano-rod composite, it is characterised in that：Step Suddenly in (5), rotating speed is 6000rpm/min during centrifugation.
- 7. the application of nickel oxide particle as claimed in claim 1/titanium dioxide nano-rod composite, it is characterised in that：Step Suddenly in (5), deionized water and absolute ethyl alcohol distinguish washing precipitate 3 times and 1 time.
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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 |
| CN108962626B (en) * | 2018-08-14 | 2021-03-26 | 东北大学 | Composite material with pn junction structure for super capacitor |
| CN109003821B (en) * | 2018-08-14 | 2021-03-26 | 东北大学 | Ultrahigh dielectric constant composite material, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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| Preparation of TiO2/NiO composite particles and their applications in dye-sensitized solar cells;Chuen-Shii Chou等;《Advanced Powder Technology》;20100312(第22期);第31-42页论文摘要试验部分第2.2、2.3节 * |
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