CN102543462A - Composite counter electrode for sensitization type solar battery and preparation method thereof - Google Patents
Composite counter electrode for sensitization type solar battery and preparation method thereof Download PDFInfo
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- CN102543462A CN102543462A CN2011103891837A CN201110389183A CN102543462A CN 102543462 A CN102543462 A CN 102543462A CN 2011103891837 A CN2011103891837 A CN 2011103891837A CN 201110389183 A CN201110389183 A CN 201110389183A CN 102543462 A CN102543462 A CN 102543462A
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- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
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Abstract
The invention relates to a composite counter electrode for a sensitization type solar battery and a preparation method thereof. The structure of the composite counter electrode is that a catalyst layer composed of amorphous carbon, a carbon nano tube and metal nano particles is developed on a conducting glass fluorinedoped tin oxide (FTO). The preparation method of the composite counter electrode is that a small amount of thiophene is added in absolute ethyl alcohol, defined amount of metallocene compound is added, mixed liquid is injected in an alcohol lamp, clean and neat FTO is fixed on a lifting table, flame is lit, the FTO stays for a time in the flame, then the flame is extinguished, and the composite counter electrode composed of the amorphous carbon, the carbon nano tube and the metal nano particles can be obtained on the FTO. The composite counter electrode is high in catalytic activity, good in stability and the like. The preparation method not only is simple in process and low in cost, and reduces manufacture cost of dye sensitization solar batteries and quantum dot sensitization solar batteries, but also is environment-friendly and applicable to industrialization production.
Description
Technical field
The present invention relates to solar battery technology, particularly relate to the compound of a kind of sensitization class solar cell electrode and preparation method are belonged to technical field of nano material, also belong to technical field of new energies.
Background technology
In recent years, the contradiction between energy problem and the global economy development becomes increasingly conspicuous, and becomes the key factor of restriction social development.DSSC is a kind of new chemical solar cell of the nineties exploitation, has less cost and simple preparation technology, and stable performance, decay are few, have good application prospects.
Sensitization class solar cell is made up of three parts: the light anode (TiO of absorbing dye
2Film), contain redox couple (I
3 -/ I
-) electrolyte and to electrode.Effect to electrode is that the electronics that external circuit flows into is passed to the I in the electrolyte
3 -, and it is reduced to I
-As the important component part of battery, to the catalytic performance of electrode electricity conversion important influence to entire cell.What adopt at present mainly is that Pt is to electrode, though Pt is low to electrode resistance, catalytic activity good.But Pt is a kind of noble metal, costs an arm and a leg, and its preparation needs high temperature or high vacuum condition and relevant device, is not suitable for large-scale application.Therefore in order to reduce cost, material with carbon element is substituted platinum electrode by people's broad research.Reported that like people such as Lin Jiapeng (the 20th the 9th phase of volume) on the China YouSe Acta Metallurgica Sinica a kind of carbon is nano combined to the application of electrode in DSSC; They add CNT to and process suspension in the nano carbon black; Be added drop-wise to the FTO high-temperature heat treatment of carrying out on glass then; Obtain nanometer carbon black-CNT composite material to electrode, obtained good effect.People such as Zhang Jun is at ElectrochimicaActa (2011 for another example; EA-16677) reported on that a kind of polythiophene class compound is to electrode; They are that the multi-walled carbon nano-tubes of 20nm is dissolved in the solution that comprises plasma water, ethanol and polyethylene glycol with diameter; Method through the oxidized zone electric polymer has prepared the composite membrane of being made up of polythiophene class compound and multi-walled carbon nano-tubes, is applied in the DSSC, has obtained 5.47% transformation efficiency.But the said method complex process needs high-temperature service, and production cost is high.Method of the present invention, raw material is cheap, and is simple for process, and it is lower that preparation condition requires, and the photoelectric properties that adopt this compound DSSC to electrode are a little more than the photoelectric properties of Pt to the DSSC of electrode.
Summary of the invention
In order to overcome the problems referred to above; The invention provides the compound of a kind of sensitization class solar cell to electrode and preparation method; Its preparation technology is simple; With low cost, the Pt that can replace sensitization class solar cell is to electrode, thereby haves laid a good foundation for the industrialization production of sensitization class solar cell.
The compound structure to electrode of said sensitization class solar cell is to mix the Catalytic Layer that one deck is made up of amorphous carbon, CNT and metal nanoparticle of having grown on the electro-conductive glass FTO of fluorine; The thickness of Catalytic Layer is 20～50 μ m, and the mass percent of described metal nanoparticle and carbon is 10%～50%.
The compound preparation method to electrode of said sensitization class solar cell is characterized in that may further comprise the steps:
(1) in absolute ethyl alcohol, add a small amount of thiophene, the concentration of adding thiophene is 0.01～1%, and this concentration is the volume ratio of thiophene and absolute ethyl alcohol;
(2) in the solution in step (1), add an amount of metallocenes, the concentration of adding metallocenes is 1～10mg/mL, injects alcolhol burner then;
(3) FTO with clean is fixed on the lifting platform, and the distance of regulating between FTO and the alcolhol burner wick top is 3～6.5cm;
(4) light alcolhol burner in the step (3), FTO is put into flame, stay for some time, knock down the flame is treated to take off after the sample cooling then, on FTO, has black precipitate to generate, and promptly obtains compound to electrode.
Described FTO time of staying in flame is 1～60s.
The invention has the advantages that: this is compound is made up of amorphous carbon, CNT and metal nanoparticle electrode; Oxidation-reduction pair there is high catalytic activity; Can improve the absorptivity of light; With Pt electrode is compared, when reducing this battery production cost, kept the high electricity conversion of this battery.Preparation method of the present invention is the alcohol catalysis firing method, and cost of material is cheap, and apparatus and process is simple, and this has effectively reduced the production cost that sensitization class solar cell is made, for good basis has been established in the industrialization production of this battery.
The present invention will be illustrated through following instance, and still, the present invention is not limited to described embodiment here, and embodiments of the invention only are used for further setting forth the present invention.Substitute, change or change what content of the present invention was carried out for those skilled in the art, these equivalent form of values fall in the application institute restricted portion equally.
Description of drawings
Fig. 1 is compound electron scanning micrograph to electrode, is vertical view (a), (b) is profile.
Fig. 2 is compound transmission electron microscope photo to electrode, (a) amplifies for low power, (b) amplifies for high power.
Fig. 3 is compound Raman spectrum to electrode.
Fig. 4 is the i-v curve comparison diagram of compound Pt to electrode and thermal decomposition method of the present invention to the DSSC of electrode assembling; The A curve is corresponding to of the present invention compound to electrode; The B curve corresponding to Pt to electrode.
Embodiment
It is of the present invention compound to electrode and preparation method to combine accompanying drawing and embodiment to specifically describe below
Embodiment 1
Compound preparation process to electrode is following:
(1) in absolute ethyl alcohol, add a small amount of thiophene, the concentration of adding thiophene is 0.1%, and this concentration is the volume ratio of thiophene and absolute ethyl alcohol;
(2) in the solution in step (1), add an amount of ferrocene, the concentration of adding ferrocene is 5mg/mL, injects alcolhol burner then;
(3) FTO with clean is fixed on the lifting platform, and the distance of regulating between FTO and the alcolhol burner wick top is 6cm;
(4) light alcolhol burner in the step (3), FTO is put into flame, stop 15s, knock down the flame is treated to take off after the sample cooling then, on FTO, has black precipitate to generate, and promptly obtains compound to electrode.
The compound of preparation is applied in the DSSC electrode, and the open circuit voltage of the DSSC of acquisition is 0.7639V, and short-circuit current density is 8.75mA/cm
2, fill factor, curve factor is 0.2768, photoelectric conversion efficiency is 1.85%.
Embodiment 2
(1) in absolute ethyl alcohol, add a small amount of thiophene, the concentration of adding thiophene is 0.1%, and this concentration is the volume ratio of thiophene and absolute ethyl alcohol;
(2) in the solution in step (1), add an amount of ferrocene, the concentration of adding ferrocene is 5mg/mL, injects alcolhol burner then;
(3) FTO with clean is fixed on the lifting platform, and the distance of regulating between FTO and the alcolhol burner wick top is 6cm;
(4) light alcolhol burner in the step (3), FTO is put into flame, stop 20s, knock down the flame is treated to take off after the sample cooling then, on FTO, has black precipitate to generate, and promptly obtains compound to electrode.
The open circuit voltage of the DSSC that obtains is 0.7839V, and short-circuit current density is 7.59mA/cm
2, fill factor, curve factor is 0.4152, photoelectric conversion efficiency is 2.47%.
Embodiment 3
(1) in absolute ethyl alcohol, add a small amount of thiophene, the concentration of adding thiophene is 0.1%, and this concentration is the volume ratio of thiophene and absolute ethyl alcohol;
(2) in the solution in step (1), add an amount of ferrocene, the concentration of adding ferrocene is 5mg/mL, injects alcolhol burner then;
(3) FTO with clean is fixed on the lifting platform, and the distance of regulating between FTO and the alcolhol burner wick top is 6cm;
(4) light alcolhol burner in the step (3), FTO is put into flame, stop 25s, knock down the flame is treated to take off after the sample cooling then, on FTO, has black precipitate to generate, and promptly obtains compound to electrode.
The open circuit voltage of the DSSC that obtains is 0.7839V, and short-circuit current density is 9.81mA/cm
2, fill factor, curve factor is 0.4304, photoelectric conversion efficiency is 3.31%.
Embodiment 4
(1) in absolute ethyl alcohol, add a small amount of thiophene, the concentration of adding thiophene is 0.1%, and this concentration is the volume ratio of thiophene and absolute ethyl alcohol;
(2) in the solution in step (1), add an amount of ferrocene, the concentration of adding ferrocene is 5mg/mL, injects alcolhol burner then;
(3) FTO with clean is fixed on the lifting platform, and the distance of regulating between FTO and the alcolhol burner wick top is 6cm;
(4) light alcolhol burner in the step (3), FTO is put into flame, stop 30s, knock down the flame is treated to take off after the sample cooling then, on FTO, has black precipitate to generate, and promptly obtains compound to electrode.
The open circuit voltage of the DSSC that obtains is 0.7940V, and short-circuit current density is 10.7mA/cm
2, fill factor, curve factor is 0.5603, photoelectric conversion efficiency is 4.76%.This compound electron scanning micrograph and transmission electron microscope photo to electrode is as depicted in figs. 1 and 2 respectively.From Fig. 2, can clearly find out this compound CNT shape and metal nanoparticle structure to electrode.Fig. 3 is compound Raman spectrum to electrode, can see at 100-2000cm from Fig. 3
-1In this frequency range, a lot of characteristic peaks occurred, the G peak, characteristic feature peak and the D peak that characterize the material with carbon element degree of graphitization have been arranged, at 100-350cm
-1Characteristic peak in the scope is the eigen vibration pattern of nanotube, and this shows and has CNT in the deposit.Compound electrode and Pt are assembled DSSC to electrode with this, its I-V curve is as shown in Figure 4 respectively, and the A curve is corresponding to of the present invention compound to electrode, the B curve corresponding to Pt to electrode.
Embodiment 5
(1) in absolute ethyl alcohol, add a small amount of thiophene, the concentration of adding thiophene is 0.1%, and this concentration is the volume ratio of thiophene and absolute ethyl alcohol;
(2) in the solution in step (1), add an amount of ferrocene, the concentration of adding ferrocene is 5mg/mL, injects alcolhol burner then;
(3) FTO with clean is fixed on the lifting platform, and the distance of regulating between FTO and the alcolhol burner wick top is 6cm;
(4) light alcolhol burner in the step (3), FTO is put into flame, stop 35s, knock down the flame is treated to take off after the sample cooling then, on FTO, has black precipitate to generate, and promptly obtains compound to electrode.
The open circuit voltage of the DSSC that obtains is 0.8121V, and short-circuit current density is 11.81mA/cm
2, fill factor, curve factor is 0.4285, photoelectric conversion efficiency is 4.11%.
Embodiment 6
(1) in absolute ethyl alcohol, add a small amount of thiophene, the concentration of adding thiophene is 0.1%, and this concentration is the volume ratio of thiophene and absolute ethyl alcohol;
(2) in the solution in step (1), add an amount of ferrocene, the concentration of adding ferrocene is 5mg/mL, injects alcolhol burner then;
(3) FTO with clean is fixed on the lifting platform, and the distance of regulating between FTO and the alcolhol burner wick top is 6cm;
(4) light alcolhol burner in the step (3), FTO is put into flame, stop 30s, knock down the flame is treated to take off after the sample cooling then, on FTO, has black precipitate to generate, and promptly obtains compound to electrode.
The TiO that silk screen printing is good
2Film under 30 ℃, the 0.3M Cd (NO that immerses earlier
3)
2The mixed solution of ethanol and water in 5min, take out then and use deionized water rinsing, then at the Na of 0.3M
25min in the ethanol of S and the mixed solution of water takes out and uses deionized water rinsing.Then repetitive cycling is 4 times, obtains the TiO after the sensitization
2The light anode, wherein the volume ratio of ethanol and water is 1: 1; It is assembled into quantum dot sensitized solar cell, and electrolyte adopts the polysulfide electrolyte, and assemble method is with embodiment 1.
The open circuit voltage of the quantum dot sensitized solar cell that obtains is 0.069V, and short-circuit current density is 0.13mA/cm
2, fill factor, curve factor is 0.33, photoelectric conversion efficiency is 0.03%.
Claims (5)
1. one kind is used for the compound to electrode of sensitization class solar cell; It is characterized in that the compound structure to electrode of said sensitization class solar cell is for to mix the Catalytic Layer that one deck is made up of amorphous carbon, CNT and metal nanoparticle of having grown on the electro-conductive glass FTO of fluorine.
2. sensitization class solar cell according to claim 1 compound to electrode is characterized in that described Catalytic Layer thickness is 20～50 μ m.
3. sensitization class solar cell according to claim 1 compound to electrode, the mass percent that it is characterized in that described metal nanoparticle and carbon is 10%～50%.
4. the compound preparation method to electrode of a sensitization class solar cell is characterized in that comprising the steps:
(1) in absolute ethyl alcohol, add a small amount of thiophene, the concentration of adding thiophene is 0.01～1%, and this concentration is the volume ratio of thiophene and absolute ethyl alcohol;
(2) in the solution in step (1), add an amount of metallocenes, the concentration of adding metallocenes is 1～10mg/mL, injects alcolhol burner then;
(3) FTO with clean is fixed on the lifting platform, and the distance of regulating between FTO and the alcolhol burner wick top is 3～6.5cm;
(4) light alcolhol burner in the step (3), FTO is put into flame, stay for some time, knock down the flame is treated to take off after the sample cooling then, on FTO, has black precipitate to generate, and promptly obtains compound to electrode.
5. by the described method of claim 4, it is characterized in that: described FTO time of staying in flame is 1～60s.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105580097A (en) * | 2014-01-30 | 2016-05-11 | 泰国研究基金会(Trf) | Catalytic carbon counter electrode for dye-sensitized solar cells |
| CN108281288A (en) * | 2018-01-17 | 2018-07-13 | 北京航空航天大学 | A kind of quantum dot sensitized solar cell is to electrode and its preparation method and application |
| CN111415822A (en) * | 2020-03-05 | 2020-07-14 | 沈阳农业大学 | Onion carbon/manganese dioxide array electrode and preparation method and application thereof |
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| CN101000934A (en) * | 2006-12-21 | 2007-07-18 | 华侨大学 | High-property metal/graphite compound counter electrode for dye sensitization solar battery and preparation method thereof |
| CN101510471A (en) * | 2009-03-03 | 2009-08-19 | 彩虹集团公司 | Method for preparing counter electrode of dye sensitization solar battery based on carbon nanotube and platinum |
| US20110171531A1 (en) * | 2009-09-08 | 2011-07-14 | Northwestern University | Multifunctional Nanocomposites of Carbon Nanotubes and Nanoparticles Formed Via Vacuum Filtration |
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Patent Citations (3)
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| CN101000934A (en) * | 2006-12-21 | 2007-07-18 | 华侨大学 | High-property metal/graphite compound counter electrode for dye sensitization solar battery and preparation method thereof |
| CN101510471A (en) * | 2009-03-03 | 2009-08-19 | 彩虹集团公司 | Method for preparing counter electrode of dye sensitization solar battery based on carbon nanotube and platinum |
| US20110171531A1 (en) * | 2009-09-08 | 2011-07-14 | Northwestern University | Multifunctional Nanocomposites of Carbon Nanotubes and Nanoparticles Formed Via Vacuum Filtration |
Non-Patent Citations (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105580097A (en) * | 2014-01-30 | 2016-05-11 | 泰国研究基金会(Trf) | Catalytic carbon counter electrode for dye-sensitized solar cells |
| CN105580097B (en) * | 2014-01-30 | 2018-10-16 | 泰国研究基金会(Trf) | Catalysis carbon for dye-sensitized solar cells is to electrode |
| CN108281288A (en) * | 2018-01-17 | 2018-07-13 | 北京航空航天大学 | A kind of quantum dot sensitized solar cell is to electrode and its preparation method and application |
| CN111415822A (en) * | 2020-03-05 | 2020-07-14 | 沈阳农业大学 | Onion carbon/manganese dioxide array electrode and preparation method and application thereof |
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Application publication date: 20120704 |