CN100479196C - Heat oxidation preparing method of cathode material of solar dye battery - Google Patents
Heat oxidation preparing method of cathode material of solar dye battery Download PDFInfo
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- CN100479196C CN100479196C CNB2007100512550A CN200710051255A CN100479196C CN 100479196 C CN100479196 C CN 100479196C CN B2007100512550 A CNB2007100512550 A CN B2007100512550A CN 200710051255 A CN200710051255 A CN 200710051255A CN 100479196 C CN100479196 C CN 100479196C
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Abstract
The invention is concerned with one dimension CuO Nano-needle/ Cu substrate material and the application in dye solar cells. The material is produced with pulse electrolysis deposition process. Electrolysis deposit one layer of nanocrystalline Cu film on Cu substrate, put this film into heating stove to get one dimension CuO Nano-needle material under 750+/-50 DEG C for 1 to 2 hours. Take the one dimension CuO Nano-needle/ Cu substrate material as cathode material to solar cell with TCO Conducting glass/ TiO2 nanocrystalline/ dry/ CuO Nano-needle/ Cu substrate, and test its efficiency of light to electricityeta. For the work function of CuO(Phi=5.3eV) is close to Pt(Phi=5.65eV), and P type of CuO has high hole mobility (0.1cm<2>V<-1>S<-1>), so it can be used as cathode material to solar cell instead of Pt to greatly reduce the cost, for better application and spread of solar cell.
Description
Technical field
The present invention relates to the synthetic of CuO nano-needle pin/Cu baseplate material and in the application of making the dye solar cell cathode material, metal nanometer material and field of nanometer technology.
Background technology
Energy shortage and environmental pollution are the two large problems that the present mankind face.Along with the great development of World Economics, particularly China's economic over nearly more than 20 years every year on average with 7%~8% speed increment, strengthened demand greatly to the energy.Yet fossil dyestuffs such as coal, oil, natural gas (or claiming primary energy) reserves on earth are limited, are not inexhaustible, nexhaustible.Moreover, use the fossil dyestuff to discharge a large amount of CO
2, N
xPollutants such as O, hydrocarbon and sulfide cause problem of environmental pollutions such as greenhouse effect, acid rain, depletion of the ozone layer, the serious harm human physical and mental health.Based on above reason, the development of new clean energy resource has caused the attention of countries in the world.
The mankind in the foreseeable following time, solar energy is as inexhaustible, the nexhaustible clear energy sources of the mankind, do not produce any environmental pollution, and be not subjected to the restriction of geographical conditions basically, so solar utilization technique research having caused various countries scientists' extensive attention.Because the tempting prospect of nanometer technology and wide economic and social benefit, the Application and Development that solar cell is combined with nanometer technology more becomes the focus of research.Current, the development of solar cell exists a both direction and a difficult problem: the one, and the light one photoelectric transformation efficiency η of raising solar cell; The 2nd, reduce the production cost of solar cell, thereby help solar cell in industrial production, people's daily life and in the extensive use and the popularization in remote areas such as rural area.But the cost that reduces dye solar cell is difficult point and its further popularization and practical bottleneck of restriction that current dye solar cell is studied with the raising photoelectric conversion efficiency.
Present research all is to concentrate on the anode material that improves solar cell, corresponding with anode material is Pt/TCO electro-conductive glass (electrically conducting transparent optical glass, fluorine doped tin oxide glass, effectively transmissivity is greater than 80%), therefore the cost of negative electrode is still expensive, and research in this regard still seldom.The present invention is nanocrystalline by electro-deposition layer of metal Cu on metal Cu substrate, at the directed CuO nano-needle needle material of air thermal oxidation preparation, and as the cathode material of dye solar cell, measures its photoelectric conversion efficiency η.This method technology is simple, low for equipment requirements, favorable reproducibility, and the controllable degree height meets environmental requirement, and greatly reduces the synthetic cost of dye solar cell, helps the further application and the popularization of dye solar cell.
Summary of the invention
Problem to be solved by this invention provides a kind of CuO nano-needle pin/Cu baseplate material and in the application of dye solar cell cathode material,
Technical scheme provided by the invention is: adopt impulse electrodeposition technology at the nanocrystalline Cu film of metal Cu substrate surface electro-deposition one deck, then nanocrystalline Cu film was heated 1-2 hour down for 750 ± 50 ℃ in temperature in air, thermal oxidation prepares the CuO nano-needle needle material.CuO nano-needle needle material/Cu the substrate that makes is " ITO electro-conductive glass/TiO as structure
2Nanocrystalline/dyestuff/CuO nanoneedle/Cu substrate " the dye solar cell cathode material, replace cathode material in traditional dye solar cell-metal Pt electrode, measure and detect the photoelectric conversion efficiency η of this dye solar cell.
Above-mentioned preparation electro-deposition is nanocrystalline, the technology characteristics and the parameter area of CuO nano-needle needle material and dye solar cell are: the pulse electrodeposition parameter is: output pulse frequency f is 100Hz, and duty ratio r is 10%; The oxidate temperature scope is 750 ± 50 ℃, 1-2 hour thermal oxidation time; Dye solar battery structure is " ITO electro-conductive glass/TiO2 nanocrystalline/dyestuff/CuO nanoneedle/Cu substrate ".
In heating 1-2 hour down of 750 ± 50 ℃ of temperature, there is the needle-like product of a large amount of arrayed in the CuO nano-needle needle material of thermal oxidation preparation to nanocrystalline Cu film in air, and its diameter is generally the 35-45 nanometer, and length is above 10 microns
((Φ's=5.65eV) is close, and while p type CuO material has very high hole mobility (0.1cm for the work function of Φ=5.3eV) and metal Pt because CuO
2V
-1S
-1), therefore, it can be used for the cathode material of solar cell by substituted metal Pt electrode, and can reduce the production cost of solar cell greatly, thereby helps the practical application and the popularization of solar cell.
The present invention adopts the nanocrystalline Cu film preparation of thermal oxidation CuO nano-needle needle material in the air, is used for the cathode material of dye solar cell, and technology is simple, and the controllable degree height meets environmental requirement, and is with low cost.
Description of drawings
The SEM figure of the CuO nano-needle pin product that Fig. 1 makes for the nanocrystalline Cu film of embodiment 1 thermal oxidation under different temperatures.(a) 700 ℃ among the figure; (b) 800 ℃; (c) 900 ℃; (d) 1000 ℃.
Fig. 2: for scheming at the SEM of the synthetic CuO nano-needle needle material of 700 ℃ of nanocrystalline Cu films of following thermal oxidation among the embodiment 1.(a) be low power SEM figure, (b) be high power SEM figure
Fig. 3: among the embodiment 1 at the photoelectric conversion efficiency I-V curves of 700 ℃ of down synthetic CuO nano-needle pins as the dye solar cell cathode material.
Embodiment
Embodiment 1:
(1) adopt impulse electrodeposition technology, taking output pulse frequency f is that 100Hz, duty ratio r are 10% pulse electrodeposition parameter, at the nanocrystalline Cu film of metal Cu substrate surface electro-deposition one deck; (2) nanocrystalline Cu film different heating-up temperature (700 ℃, 800 ℃, 900 ℃, 1000 ℃) in air was heated 1-2 hour down, thermal oxidation prepares the CuO nano-needle pin, and ESEM (SEM) experimental result is ((a) 700 ℃ among the figure as shown in Figure 1; (b) 800 ℃; (c) 900 ℃; (d) 1000 ℃); (3) with heating-up temperature be the cathode materials (the SEM experimental result of cathode material as shown in Figure 2) of 700 ℃ of CuO nano-needle needle material/Cu substrates that prepare down, TiO as dye solar cell
2Nanocrystalline material is as anode material, and process bipyridyl ruthenium dye (N
3, (Bu4N)
2Ru (dcbpyH)
2(NCS)
2) the ethanol solution sensitization handle, adopt liquid electrolyte (LiI, I
2Be dissolved in 3-methoxypropionitrile (MePN, tetra-tert pyridine (4-erbutylpridine) 3-methoxypropionitrile)), be assembled into the dye solar cell of structure for " ITO electro-conductive glass/TiO2 nanocrystalline/dyestuff/CuO nanoneedle/Cu substrate "; (4) under the simulated solar irradiation of a dosage (100 milliwatts/centimetre
2), the photoelectric conversion efficiency η (I-V relation) of the dye solar cell of employing photometer measurement and this structure of detection, photoelectric conversion efficiency I-V curve is seen accompanying drawing 3.
Can realize the nanocrystalline Cu film preparation of thermal oxidation CuO nano-needle needle material with reference to the method for embodiment 1 and in the application of dye solar cell cathode material by above experiment parameter.
Embodiment 1 Fig. 1 illustrates that the SEM figure of synthetic product shows under 700 ℃, 800 ℃, can prepare cupric oxide nano pin array a large amount of, proper alignment; Along with temperature raises, the density of nanoneedle is more and more lower, the cluster shape particle that a large amount of fused deposition of simultaneous produces.
Fig. 2 Fig. 2 (a) is low power SEM figure, and Fig. 2 (b) is high power SEM figure, and this shows that there is the needle-like product of a large amount of arrayed in synthetic product, and its diameter is generally the 35-45 nanometer, and length is above 10 microns.
Fig. 3 I-V curve shows that the CuO nano-needle pin is 1.12% as the photoelectric conversion efficiency of dye solar cell cathode material, and fill factor, curve factor is 0.37.
Claims (2)
1, a kind of thermal oxidation preparation method of dye solar cell cathode material is characterized in that preparation process comprises:
(1) adopt impulse electrodeposition technology at the nanocrystalline Cu film of metal Cu substrate surface electro-deposition one deck;
(2) with nanocrystalline Cu film in air 750 ± 50 ℃ the heating 1-2 hour, thermal oxidation prepares the CuO nano-needle pin, makes CuO nano-needle pin/Cu board structure material, is the cathode material of making dye solar cell.
2, the thermal oxidation preparation method of dye solar cell cathode material according to claim 1 is characterized in that: the pulse electrodeposition parameter when preparing this dye solar cell cathode material is: output pulse frequency f is 100Hz, and duty ratio r is 10%.
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CNB2007100512550A CN100479196C (en) | 2007-01-12 | 2007-01-12 | Heat oxidation preparing method of cathode material of solar dye battery |
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CN100479196C true CN100479196C (en) | 2009-04-15 |
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Families Citing this family (5)
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CN102127779B (en) * | 2010-12-25 | 2012-08-22 | 太原理工大学 | Method for preparing copper oxide nano tube |
CN106892061A (en) * | 2017-02-17 | 2017-06-27 | 上海源紊新能源科技有限公司 | A kind of buoy that can utilize wind energy and solar energy |
CN107369729B (en) * | 2017-08-08 | 2019-02-12 | 湖州师范学院 | A kind of nano ordered interpenetrating total oxygen compound hetero-junction thin-film solar cell and preparation method thereof |
CN107705993B (en) * | 2017-08-21 | 2019-01-08 | 湖州师范学院 | Dye-sensitized solar cells cupric oxide nano-rod array is to electrode and preparation method thereof |
CN111564592B (en) * | 2020-05-21 | 2022-07-29 | 贵州梅岭电源有限公司 | High-specific-power single thermal battery and preparation method thereof |
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2007
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Non-Patent Citations (6)
Title |
---|
CuO nanowires can be synthesized by heating copper substrates in air. Xuchuan Jiang等.Nano Letters,Vol.2 No.12. 2002 |
CuO nanowires can be synthesized by heating copper substrates in air. Xuchuan Jiang等.Nano Letters,Vol.2 No.12. 2002 * |
Room temperature growth of CuO nanorod arrays on copper and their application as a cathode in dye-sensitized solar cells. Sambandam Anandan等.Materials Chemistry and Physics,Vol.93 No.1. 2005 |
Room temperature growth of CuO nanorod arrays on copper and their application as a cathode in dye-sensitized solar cells. Sambandam Anandan等.Materials Chemistry and Physics,Vol.93 No.1. 2005 * |
利用电沉积铁纳米晶热氧化法制备铁氧化物纳米针研究. 刘曰利等.纳米科技,第3卷第4期. 2006 |
利用电沉积铁纳米晶热氧化法制备铁氧化物纳米针研究. 刘曰利等.纳米科技,第3卷第4期. 2006 * |
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