CN102568850B - Dye sensitized solar cell photoanode, cell and manufacturing method of photoanode - Google Patents
Dye sensitized solar cell photoanode, cell and manufacturing method of photoanode Download PDFInfo
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- CN102568850B CN102568850B CN201210014335.XA CN201210014335A CN102568850B CN 102568850 B CN102568850 B CN 102568850B CN 201210014335 A CN201210014335 A CN 201210014335A CN 102568850 B CN102568850 B CN 102568850B
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- tio
- substrate
- solar cell
- sensitized solar
- nanometer
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Links
- 238000004519 manufacturing process Methods 0.000 title abstract 3
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 239000002071 nanotube Substances 0.000 claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 52
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 230000005540 biological transmission Effects 0.000 abstract description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- 239000000975 dye Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000000608 laser ablation Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E10/549—Organic PV cells
Landscapes
- Hybrid Cells (AREA)
- Photovoltaic Devices (AREA)
Abstract
The invention relates to a dye sensitized solar cell photoanode, a cell and a manufacturing method of the photoanode. The dye sensitized solar cell photoanode comprises a Ti substrate, a TiO2 nano grid layer and a TiO2 nanotube array, wherein the TiO2 nano grid layer is positioned on the Ti substrate; nanotubes of the TiO2 nanotube array respectively grow on the Ti substrate and pass through the TiO2 nano grid layer. According to the dye sensitized solar cell photoanode, the cell and the manufacturing method of the photoanode, the adsorption capability of TiO2 to dye is improved, and thus the performance of the dye sensitized solar cell photoanode is improved; in addition, electrons can be captured by the TiO2 nanotubes, and the electron transmission rate is increased.
Description
Technical field
The present invention relates to technical field of solar batteries, particularly relate to the preparation method of dye-sensitized solar cell anode, battery and this dye-sensitized solar cell anode.
Background technology
DSSC is third generation thin-film solar cells.Its major part is the TiO of high-specific surface area
2film, can chemisorbed have the dyestuff of strong absorption coefficient to sunlight and penetrate described TiO
2film the electrolyte matched with the oxidation-reduction potential of dyestuff.But the electron transfer rate of current DSSC is low.
Summary of the invention
The problem that the present invention solves is the problem that existing DSSC electron transfer rate is low.
For solving the problem, the invention provides a kind of dye sensitization of solar light anode, this light anode comprises Ti substrate, TiO
2nanometer grid layer and TiO
2nano-tube array, described TiO
2nanometer grid layer is positioned in Ti substrate, described TiO
2the nanotube of nano-tube array is respectively from described Ti substrate grown and through described TiO
2nanometer grid layer.
Alternatively, described TiO
2the grid line width of nanometer grid layer is 0.01 ~ 0.05mm, and spacing is 0.01 ~ 0.05mm.
Alternatively, described TiO
2the thickness of nano-tube array is 300 ~ 500nm.
The present invention also provides a kind of DSSC, the aforementioned dye-sensitized solar cell anode described in any one of this battery.
The present invention also provides the method preparing abovementioned dyes sensitization solar light anode, and the method comprises the steps: that a. cleans Ti substrate; B. the Ti substrate after cleaning is placed in the TiCl that concentration is 40 ~ 50mmol/L
4in solution, in the water-bath at 70 DEG C, process 15 ~ 30min, form TiO
2nanometer layer; C. the described TiO that b step is formed is etched
2nanometer layer and form TiO
2nanometer grid layer; D. by NaHSO
4h
2o, C
6h
5na
3o
72H
2o and NaF presses amount of substance and mixes than 2 ~ 4: 2: 1 ~ 2 and regulate with HF, is configured to the weakly acidic electrolyte that pH value is 5.0 ~ 6.0; E. TiO will be had
2the Ti substrate of nanometer grid layer is as anode, and platinum is that negative electrode is placed in the obtained described electrolyte of Step d, and is 10V ~ 25V at voltage, and temperature is under the condition of 10 DEG C ~ 20 DEG C, carries out magnetic agitation 10 ~ 20min, obtains described TiO
2nano-tube array; F. by described, there is TiO
2the Ti substrate of nano-tube array is placed in Muffle furnace, is warming up to 450 ~ 500 DEG C, and process 15 ~ 30min obtains described dye-sensitized solar cell anode.
Alternatively, clean described Ti substrate and adopt following steps: adopt acetone and deionized water successively to clean described Ti substrate 10min; By the Ti substrate of being crossed by Ultrasonic Cleaning at HF and HNO
3volume ratio is chemical polishing in the mixed liquor of 1: 1; Acetone and deionized water Ti substrate after polishing is successively adopted to carry out ultrasonic cleaning 10min, rear low temperature drying again.
Compared with prior art, the present invention has the following advantages:
Owing to the present invention includes TiO
2nanometer grid layer and TiO
2nanotube array layer, and TiO
2nanometer grid layer adds the specific area of nano-pipe array thin film, and improves TiO
2to the adsorption capacity of dyestuff, thus improve the performance of dye-sensitized cell, in addition, electronics can pass through described TiO
2nanotube is captured, so electric transmission path is short, and electron transfer rate is high.
Accompanying drawing explanation
Fig. 1 is grating structure signal in the Ti substrate that formed of the present invention;
Fig. 2 is the structural representation of dye-sensitized solar cell anode of the present invention;
Fig. 3 is the SEM structure chart of dye-sensitized solar cell anode of the present invention.
Drawing reference numeral illustrates:
1-Ti substrate, 2-TiO
2nanometer grid layer, 3-TiO2 grid space, 4-TiO2 nano-tube array.
Embodiment
By describing technology contents of the present invention, structural feature in detail, reached object and effect, accompanying drawing is coordinated to be described in detail below in conjunction with embodiment.
Refer to Fig. 1 and Fig. 2 and composition graphs 3, dye-sensitized solar cell anode of the present invention comprises Ti substrate 1, TiO
2nanometer grid layer 2, TiO
2grid space 3 and TiO
2nano-tube array 4.Described TiO
2nanometer grid layer 2 comprises grid line and TiO
2grid space 3, is formed in described Ti substrate 1, in the present embodiment, is formed at the TiO in Ti substrate 1 through laser ablation
2nanometer layer and being formed.Described TiO
2the nanotube of nano-tube array 4 grows from described Ti substrate 1 respectively and passes described TiO
2nanometer grid layer 2, specifically through described TiO
2grid space 3.In the embodiment do not limited, described TiO
2the grid line width of nanometer grid layer 2 is 0.01 ~ 0.05mm, spacing (TiO
2grid space 3) be 0.01 ~ 0.05mm.The present inventor finds in research process, and line width and spacing directly can affect the TiO of preparation
2nano-tube array is arranged, thus affect the adsorption efficiency of dyestuff, the electricity conversion of reduction battery, and the grid line width in above-mentioned scope and spacing can effective control TiO
2nano-tube array is arranged, and improves the adsorption efficiency of dyestuff to greatest extent, Dye Adsorption can be caused not enough or excessive, improve the electricity conversion of battery below or above grid line scope.Preferably, described grid line width is 0.05mm, and spacing is 0.05mm, when grid line width and spacing are 0.05mm, 0.05mm respectively, and can not only effective control TiO
2nano-tube array is arranged, and improves the adsorption efficiency of dyestuff to greatest extent, improves the electricity conversion of battery, effectively can also simplify the light anode preparation technology of battery.The TiO formed
2the thickness of nano-tube array is 300 ~ 500nm, the present inventor finds in research process, the too low meeting of film thickness causes short circuit current to reduce, too high, increase electron recombination, reduce the electricity conversion of battery, can effectively improve battery short circuit electric current when thickness is in above-mentioned scope, reduce electron recombination.
The present invention also provides a kind of preparation method of dye-sensitized solar cell anode, below by two embodiments, the method is described.
First embodiment
Cleaning Ti substrate: this Ti substrate is Ti paper tinsel plate, by this Ti substrate priority acetone and each ultrasonic cleaning 10min of deionized water, then, at HF and HNO
3chemical polishing in the mixed liquor of volume ratio 1: 1, then, with deionized water and acetone cleaning Ti paper tinsel plate, finally, low temperature drying.
Form TiO
2nanometer layer: the TiCl described Ti substrate being soaked in 40mmol/L
4in solution, water bath processing 30min post-drying at being warming up to 70 DEG C.
Form TiO
2grid layer: adopt the TiO that laser ablation is formed
2nanometer layer, exposes Ti substrate, thus, form described TiO
2grid layer, grid line width 0.05mm, spacing is 0.05mm.
Configuration electrolyte: this electrolyte is by NaHSO
4h
2o, C
6h
5na
3o
72H
2o and NaF mixes than 2: 2: 1 by amount of substance, then regulates with HF and is configured to pH for 5.0.In other examples, the pH value of described electrolyte is between 5.0 ~ 6.0, and the electrolyte of this ratio can prepare compound standard point TiO2 nano-tube array.
Form described TiO
2nano-tube array: will TiO be had
2the Ti substrate of nanometer grid layer is as anode, and platinum, as negative electrode, is vertically placed in electrolyte, and maintenance voltage stabilization is 15V, at the temperature of 10 DEG C, after carrying out magnetic agitation 15min, is taken out by Ti paper tinsel plate, cleaning, oven dry.
Sintering: will TiO be had
2the Ti substrate of nano-tube array is placed in Muffle furnace, is warming up to 500 DEG C, and constant temperature process 30 minutes, obtains described dye-sensitized solar cell anode.
Embodiment two
Cleaning Ti substrate: this Ti substrate is Ti paper tinsel plate, by this Ti substrate priority acetone and each ultrasonic cleaning 10min of deionized water, then, at HF and HNO
3chemical polishing in the mixed liquor of volume ratio 1: 1, then, with deionized water and acetone cleaning Ti paper tinsel plate, finally, low temperature drying.
Form TiO
2nanometer layer: the TiCl described Ti substrate being soaked in 40mmol/L
4in solution, water bath processing 30min post-drying at being warming up to 70 DEG C.
Form TiO
2grid layer: adopt the TiO that laser ablation is formed
2nanometer layer, exposes Ti substrate, thus, form described TiO
2grid layer, grid line width 0.05mm, spacing is 0.05mm.
Configuration electrolyte: this electrolyte is by NaHSO
4h
2o, C
6h
5na
3o
72H
2o and NaF mixes than 4: 2: 1 by amount of substance, then regulates pH for 5.0 with HF.
Form described TiO
2nano-tube array: will TiO be had
2nanometer layer and TiO
2the Ti substrate of grid layer is as anode, and platinum, as negative electrode, is vertically placed in electrolyte, and maintenance voltage stabilization is 20V, at the temperature of 10 DEG C, after carrying out magnetic agitation 15min, is taken out by Ti paper tinsel plate, cleaning, oven dry.
Sintering: will TiO be had
2the Ti substrate of nano-tube array is placed in Muffle furnace, is warming up to 500 DEG C, and constant temperature process 30 minutes, obtains described dye-sensitized solar cell anode.
As the change of above-mentioned two embodiments, at formation TiO
2in the step of nanometer layer, described TiCl
4concentration can select in the scope of 40 ~ 50mmol/L, the processing time can be 15 ~ 30min in a water bath.In the step of configuration electrolyte, by NaHSO
4h
2o, C
6h
5na
3o
72H
2o and NaF presses amount of substance than 2 ~ 4: 2: 1 ~ 2.At formation TiO
2in the step of nano-tube array, can be 10V ~ 25V at voltage, temperature be under the condition of 10 DEG C ~ 20 DEG C, carries out magnetic agitation 10 minutes ~ 20 minutes.In the step of sintering, the temperature of Muffle furnace can be 450 ~ 500 DEG C, process 15 ~ 30min.
Claims (2)
1. a preparation method for dye-sensitized solar cell anode, described dye-sensitized solar cell anode comprises: Ti substrate, TiO
2nanometer grid layer and TiO
2nano-tube array, described TiO
2nanometer grid layer is positioned in Ti substrate, described TiO
2the nanotube of nano-tube array is respectively from described Ti substrate grown and through described TiO
2nanometer grid layer; Described TiO
2the grid line width of nanometer grid layer is 0.01 ~ 0.05mm, and grating spacing is 0.01 ~ 0.05mm; Described TiO
2the thickness of nano-tube array is 300 ~ 500nm;
It is characterized in that: the method comprises the steps:
A. Ti substrate is cleaned;
B. the Ti substrate after cleaning is placed in the TiCl that concentration is 40 ~ 50mmol/L
4in solution, in the water-bath at 70 DEG C, process 15 ~ 30min, form TiO
2nanometer layer;
C. the TiO that b step is formed is etched
2nanometer layer, Ti substrate forms TiO
2grid layer;
D. by NaHSO
4h
2o, C
6h
5na
3o
72H
2o and NaF presses amount of substance and mixes than 2 ~ 4:2:1 ~ 2 and regulate with HF, is configured to the weakly acidic electrolyte that pH value is 5.0 ~ 6.0;
E. TiO will be had
2the substrate of nanometer grid layer is as anode, and platinum is the electrolyte that negative electrode is placed in Step d and prepares, and is 10V ~ 25V at voltage, and temperature is under the condition of 10 DEG C ~ 20 DEG C, carries out magnetic agitation 10 minutes ~ 20 minutes, obtains described TiO
2nano-tube array;
F. by described, there is TiO
2the Ti substrate of nano-tube array is placed in Muffle furnace, is warming up to 450 ~ 500 DEG C, process 15 ~ 30min, the TiO of obtained Anatase
2rete, as dye-sensitized solar cell anode.
2. the preparation method of dye-sensitized solar cell anode according to claim 1, is characterized in that: clean described Ti substrate and adopt following steps:
A. Ti substrate 10min described in acetone and deionized water successively ultrasonic cleaning is adopted;
The Ti substrate of b. being crossed by Ultrasonic Cleaning is at HF and HNO
3volume ratio is chemical polishing in the mixed liquor of 1:1;
C. acetone and deionized water the Ti substrate after polishing is successively adopted to carry out ultrasonic cleaning 10min, rear low temperature drying again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210014335.XA CN102568850B (en) | 2012-01-17 | 2012-01-17 | Dye sensitized solar cell photoanode, cell and manufacturing method of photoanode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210014335.XA CN102568850B (en) | 2012-01-17 | 2012-01-17 | Dye sensitized solar cell photoanode, cell and manufacturing method of photoanode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102568850A CN102568850A (en) | 2012-07-11 |
| CN102568850B true CN102568850B (en) | 2015-01-07 |
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| CN201210014335.XA Expired - Fee Related CN102568850B (en) | 2012-01-17 | 2012-01-17 | Dye sensitized solar cell photoanode, cell and manufacturing method of photoanode |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103479215A (en) * | 2013-09-10 | 2014-01-01 | 昆山新金福精密电子有限公司 | Solar and electric kettle |
| CN112844349B (en) * | 2019-11-28 | 2023-05-05 | 桂林理工大学 | Method for preparing TiOx photo-anode by utilizing laser etching Ti sheet |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101950687A (en) * | 2010-10-22 | 2011-01-19 | 电子科技大学 | Blanket type light anode for dye sensitized solar cell and preparation method thereof |
| CN101969109A (en) * | 2010-08-03 | 2011-02-09 | 襄樊学院 | Preparation process of dendritic titanium dioxide nanotube array electrode |
| CN102263171A (en) * | 2011-06-24 | 2011-11-30 | 清华大学 | Epitaxial substrate, preparation method for epitaxial substrate and application of epitaxial substrate as grown epitaxial layer |
| CN102306550A (en) * | 2011-06-03 | 2012-01-04 | 厦门大学 | Method for preparing nano-branched titanium dioxide photoanode of dye sensitized solar cell |
| CN102320653A (en) * | 2011-05-26 | 2012-01-18 | 南京工业大学 | Anisotropic etching light trapping V-type micro-nano structure titanium dioxide material and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100269894A1 (en) * | 2009-04-28 | 2010-10-28 | Board Of Regents Of The Nevada System Of Higher Education, On Behalf Of The University Of Nevada | Titanium dioxide nanotubes and their use in photovoltaic devices |
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2012
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101969109A (en) * | 2010-08-03 | 2011-02-09 | 襄樊学院 | Preparation process of dendritic titanium dioxide nanotube array electrode |
| CN101950687A (en) * | 2010-10-22 | 2011-01-19 | 电子科技大学 | Blanket type light anode for dye sensitized solar cell and preparation method thereof |
| CN102320653A (en) * | 2011-05-26 | 2012-01-18 | 南京工业大学 | Anisotropic etching light trapping V-type micro-nano structure titanium dioxide material and application thereof |
| CN102306550A (en) * | 2011-06-03 | 2012-01-04 | 厦门大学 | Method for preparing nano-branched titanium dioxide photoanode of dye sensitized solar cell |
| CN102263171A (en) * | 2011-06-24 | 2011-11-30 | 清华大学 | Epitaxial substrate, preparation method for epitaxial substrate and application of epitaxial substrate as grown epitaxial layer |
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