CN101950687A - Blanket type light anode for dye sensitized solar cell and preparation method thereof - Google Patents
Blanket type light anode for dye sensitized solar cell and preparation method thereof Download PDFInfo
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- CN101950687A CN101950687A CN2010105163191A CN201010516319A CN101950687A CN 101950687 A CN101950687 A CN 101950687A CN 2010105163191 A CN2010105163191 A CN 2010105163191A CN 201010516319 A CN201010516319 A CN 201010516319A CN 101950687 A CN101950687 A CN 101950687A
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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
- 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
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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
- 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
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a blanket type light anode for a dye sensitized solar cell and a preparation method thereof, which belong to the technical field of solar cells. In the blanket type light anode for the dye sensitized solar cell, a layer of blanket type structure, namely a titanium dioxide nano linear array film is increased on the basis of the conventional multiporous titanium dioxide nanocrystalline film light anode. Due to the existence of a titanium dioxide nano linear array, more fuel sensitizing agents can be adsorbed; at the same time, because multiporous titanium dioxide nanocrystal interfaces are greatly reduced, crystal boundary potential barriers which need to be overcome during electronic transmission are reduced to accelerate the effective separation of photoelectron-cavity pairs in dye molecules; the multiporous titanium dioxide nanocrystalline film at the bottom can effectively reduce leakage current and dark current; and the blanket type light anode for the dye sensitized solar cell provided by the invention has higher photoelectric conversion efficiency. The preparation method has the advantages of simpleness, mild reaction condition and safe and reliable process.
Description
Technical field
The invention belongs to technical field of solar batteries, the light anode (work electrode) that relates to DSSC with and preparation method thereof.
Background technology
The energy is All Around The World development and the most basic actuating force of economic growth, is the basis that the mankind depend on for existence.The human use's mainly is primary energy at present, comprises resources such as coal, oil, natural gas, and through the consumption of human last 100 years, these non-renewable resources have been consumed in a large number, is faced with to be about to exhausted danger.The development of new regenerative resource is imperative, and novel renewable energy mainly comprises solar energy, wind energy, geothermal energy, biological energy source, Hydrogen Energy etc., wherein the application potential maximum of solar energy.One of important channel of development and utilization solar energy is to utilize solar cell that luminous energy is converted into electric energy.According to solar cell material therefor difference, can be divided into crystal silicon solar energy battery, non-crystal silicon solar cell and DSSC.Wherein, advantage such as it is simple relatively that DSSC has preparation technology, cheap is compared with the traditional silicon battery, has tangible price advantage.
DSSC is mainly by the nano porous semiconductor film that has adsorbed dye sensitizing agent (light anode), redox electrolytes matter, partly form electrode etc.Compare with traditional silicon solar cell, the characteristics of dye-sensitized solar cells maximum are that the absorption of light and the generation and the transportation of electronics are to be finished by two parts of battery.Dye sensitizing agent absorbs sunlight, and light anode and electrolyte are responsible for the transmission in electronics and hole respectively.Dye sensitizing agent is excited by sunlight, electronics by ground state transition to excitation state; The dye molecule of excitation state is injected into electronics in the semi-conductive conduction band, and the electronics in the conduction band transfers to light anode (work electrode) in nanocrystalline networks, enter external circuit; The dyestuff that loses electronics is reduced by the reducing agent in the electrolyte (mainly being the I-ion), and dyestuff has obtained regeneration like this, and the reducing agent in the electrolyte is oxidized simultaneously (mainly is I
3 -); Oxidizability ion in the electrolyte (mainly is I
3 -) be diffused into obtaining electronics on the electrode, electrolyte has obtained regeneration like this, has so just finished a circulation of photoelectric current.
The basic structure of existing dye-sensitized solar cell anode is the poriferous titanium dioxide nano-crystal film that is made in transparent conductive glass surface, and porous titanium dioxide nano-crystal film surface is the absorbing dye sensitizer again.Existing dye-sensitized solar cell anode, it is born in the poriferous titanium dioxide nano-crystal film of separation of charge and electronics transportation, owing to exist a large amount of interface resistances between the titanium dioxide nanocrystalline grain, can form the energy barrier of electron transport, limited the fast transferring of oxide conduction band electron in oxide porous network thin-film, thereby make that light induced electron-hole has restricted the raising of DSSC photoelectric conversion efficiency to not separating effectively in the dye molecule.And DSSC wants finally to replace silicon solar cell, and outside its cost advantage, improving its photoelectric conversion efficiency is the key technology bottleneck that must break through.
Summary of the invention
The invention provides a kind of used by dye sensitization solar battery blanket type light anode, this light anode is on the basis of existing used by dye sensitization solar battery poriferous titanium dioxide nano-crystal film light anode, increased one deck blanket type structure, promptly increased the layer of titanium dioxide nano-wire array film on poriferous titanium dioxide nano-crystal film surface, thereby absorbing dye sensitizer more, poriferous titanium dioxide nanocrystal interface significantly reduces simultaneously, making electronics transmit the granular boundary that will pass through in titanium dioxide nano thread significantly reduces, so just significantly reduce the crystal boundary energy barrier that electron transport will overcome, quickened the right effective separation in light induced electron-hole in the dye molecule.And the nano-porous film of this structural base can effectively reduce the generation of leakage current and dark current, so new structure light sun is expected to obviously improve the photoelectric conversion efficiency of dye-sensitized cell.The present invention provides the preparation method of described used by dye sensitization solar battery blanket type light anode simultaneously.
The technical scheme that the present invention takes is as follows:
A kind of used by dye sensitization solar battery blanket type light anode as shown in Figure 1, comprises electro-conductive glass 5, poriferous titanium dioxide nano-crystal film 4 and blanket type structure sheaf 3, and poriferous titanium dioxide nano-crystal film 4 is between electro-conductive glass 5 and blanket type structure sheaf 3.Described blanket type structure sheaf is the nano-wire array film of titanium dioxide that one deck has adsorbed dye sensitizing agent.
A kind of preparation method of used by dye sensitization solar battery blanket type light anode comprises the steps:
Step 1: prepare colloidal tio 2.
Step 2: the preparation of metatitanic acid nano-wire array film.
The strong base solution (NaOH or KOH) that metallic titanium plate is put into 100～200 ℃ reacted 1～50 hour, thereby generated one deck titanate nano-wire array film, i.e. titanium base titanate nano-wire array film in pickling metal titanium plate; Then titanium base titanate nano-wire array film is put into dilute hydrochloric acid solution and fully soak, white film and substrate up to the surface break away from, and the white film that obtains is exactly the metatitanic acid nano-wire array film.
Step 3: gluing-bonding-sintering-absorption.
At first at the prepared colloidal tio 2 of conductive glass surface coating step 1; Metatitanic acid nano-wire array film with step 2 gained is bonded in above the colloidal tio 2 then, obtains the laminated film of poriferous titanium dioxide nano-crystal film and nano-wire array film of titanium dioxide after drying in 200～600 ℃ of following sintering; At last laminated film is soaked in absorbing dye sensitizer in the dye sensitization agent solution, obtains final used by dye sensitization solar battery blanket type light anode.
Need to prove, in the technique scheme:
1) colloidal tio 2 described in the step 1 can adopt commercially available P25 colloidal tio 2, or adopts hydrothermal synthesis method to prepare voluntarily; If adopt hydrothermal synthesis method to prepare voluntarily, its preparation process is as follows: adopt metatitanic acid tetrem propyl ester [Ti (i-OC
3H
7)
4], nitric acid (HNO
3), glacial acetic acid (CH
3COOH) and deionized water (H
2O) be raw material, control Ti (i-OC
3H
7)
4, HNO
3, CH
3COOH and H
2The mol ratio of O is 1: 2.8: 1: 76; At first with Ti (i-OC
3H
7)
4Be dissolved in H
2Among the O, the powerful stirring adds CH down
3COOH slowly adds HNO more while stirring
3Then reaction system is heated to 80 ℃ and change in the autoclave, hydro-thermal reaction under the pressure condition of 150～300 ℃ temperature and 0～330Mpa obtains TiO 2 sol; At last TiO 2 sol is added high molecular surfactant after vaccum dewatering is handled and regulate viscosity, obtain thick colloidal tio 2.
2) reaction mechanism of step 2 preparation metatitanic acid nano-wire array film: metallic titanium plate forms the titanate of laminated structure under the high-concentration sodium hydroxide effect, the titanate of laminated structure curls along [101] direction gradually, form the titanate nano-wire array at last, chemical reaction wherein is Ti+NaOH → Na
2Ti
xO
2x+ 1+H
2Titanate the nano-wire array sodium ion in the titanate and the hydrogen ion in the hydrochloric acid in the dilute hydrochloric acid solution immersion process carry out ion-exchange, obtain the metatitanic acid nano-wire array; Its reaction is: Na
2Ti
xO
2x+1+ HCl → H
2Ti
xO
2x+1+ NaCl
3) in the sintering process of step 3, form titanium dioxide nanowire array after the dehydration of metatitanic acid nano-wire array, its reaction is: H
2Ti
xO
2x+1→ TiO
2+ H
2O
The invention has the beneficial effects as follows:
With respect to the nanocrystalline photo-anode film of traditional poriferous titanium dioxide, used by dye sensitization solar battery blanket type light anode provided by the invention is on the basis of existing used by dye sensitization solar battery light anode, increased one deck blanket type structure-nano-wire array film of titanium dioxide, thus absorbing dye sensitizer more; Significantly reduce owing to poriferous titanium dioxide nanocrystal interface simultaneously, making electronics transmit the crystal grain boundary that will pass through in titanium dioxide nano thread significantly reduces, so just significantly reduce the crystal boundary energy barrier that electron transport will overcome, thereby quickened the right effective separation in light induced electron-hole in the dye molecule; At last, the poriferous titanium dioxide nano-crystal film bottom the used by dye sensitization solar battery blanket type light anode provided by the invention can effectively reduce the generation of leakage current and dark current.In sum, used by dye sensitization solar battery blanket type light anode provided by the invention has higher photoelectric conversion efficiency, and (experiment test proves, adopt the DSSC of used by dye sensitization solar battery blanket type light anode assembling provided by the invention, its photoelectric conversion efficiency exceeds more than 10% than the photoelectric conversion efficiency of the DSSC that adopts the existing nanocrystalline smooth anode of poriferous titanium dioxide to assemble under other equal conditions); And the preparation method is simple, the reaction condition gentleness, and process safety is reliable.
Description of drawings
Fig. 1 is the structural representation of used by dye sensitization solar battery blanket type light anode provided by the invention.Wherein 5 is electro-conductive glass, the 4th, and poriferous titanium dioxide nano-crystal film, the 3rd, nano-wire array film of titanium dioxide.
Fig. 2 is for adopting the DSSC structural representation of used by dye sensitization solar battery blanket type light anode of the present invention.Wherein: the 1st, to electrode; The 2nd, electrolyte (iodo)
Fig. 3 is the SEM figure of used by dye sensitization solar battery blanket type light anode of the present invention.
Fig. 4 is the photoelectric current voltage curve of the DSSC of employing used by dye sensitization solar battery blanket type light anode of the present invention.
Embodiment
The preparation process of the described used by dye sensitization solar battery blanket type of following examples light anode is not to be limitation of the invention further, just, provided a kind of concrete execution mode and specified technique effect of the present invention for the convenience of compare test.Should illustrate, every according to or the used by dye sensitization solar battery blanket type light anode that comes down to specifically to prepare according to technical scheme described in the summary of the invention of front all can solve technical problem of the present invention and can reach technique effect of the present invention.
Embodiment one
The high purity titanium plate is put into 8M, 150 ℃ NaOH solution, reacted 24 hours, prepare titanium base titanate nano-wire array film, the titanium base titanate nano-wire array film that generates is put into 0.05mol/L watery hydrochloric acid fully to be soaked, white film and substrate up to the surface break away from, and obtain the metatitanic acid nano-wire array film; Be coated with the sticky shape P25 of last layer titanium oxide colloid at transparent conductive glass surface by knife coating, then the metatitanic acid nano-wire array film is adhered to the colloidal tio 2 surface, after drying, 300 ℃ of following sintering obtained the laminated film of poriferous titanium dioxide nano-crystal film and nano-wire array film of titanium dioxide in 50 minutes; At last laminated film is soaked in 4 * 10
-4Soaked 8 hours in the organic solution of the dyestuff of mol/L, obtain final used by dye sensitization solar battery blanket type light anode.
The electro-conductive glass of prepared used by dye sensitization solar battery blanket type light anode and iodine/lithium iodide electrolyte and platinum plating is assembled into battery to electrode, and carries out the photoelectric properties test.Its test result is shown in the solid line among Fig. 3, and can calculate and adopt the short circuit current of the described used by dye sensitization solar battery blanket type of present embodiment light anode cell is 15.2mA/cm
2, open circuit voltage is 0.71V, and fill factor, curve factor is 0.608, and electricity conversion is 6.58%.
The comparative example
Adopt with the same P25 colloidal tio 2 of implementation column to prepare the nanocrystalline smooth anode of poriferous titanium dioxide, and electrode is assembled into battery, and carry out the photoelectric properties test with the electro-conductive glass of iodine/lithium iodide electrolyte and platinum plating.Its test result is shown in the dotted line among Fig. 3, and can calculate and adopt the short circuit current of the nanocrystalline smooth anode cell of the described used by dye sensitization solar battery poriferous titanium dioxide of comparative example is 13.5mA/cm
2, open circuit voltage is 0.70V, and fill factor, curve factor is 0.600, and electricity conversion is 5.67％。As seen, adopt the short circuit current of the battery of used by dye sensitization solar battery blanket type light anode provided by the invention to improve 12%, photoelectric conversion efficiency has improved 14%.
Claims (5)
1. used by dye sensitization solar battery blanket type light anode, it is characterized in that, comprise electro-conductive glass (5), poriferous titanium dioxide nano-crystal film (4) and blanket type structure sheaf (3), poriferous titanium dioxide nano-crystal film (4) is positioned between electro-conductive glass (5) and the blanket type structure sheaf (3); Described blanket type structure sheaf is the nano-wire array film of titanium dioxide that one deck has adsorbed dye sensitizing agent.
2. the preparation method of a used by dye sensitization solar battery blanket type light anode comprises the steps:
Step 1: prepare colloidal tio 2;
Step 2: the preparation of metatitanic acid nano-wire array film;
The strong base solution that metallic titanium plate is put into 100～200 ℃ reacted 1～50 hour, thereby generated one deck titanate nano-wire array film, i.e. titanium base titanate nano-wire array film in pickling metal titanium plate; Then titanium base titanate nano-wire array film is put into dilute hydrochloric acid solution and fully soak, white film and substrate up to the surface break away from, and the white film that obtains is exactly the metatitanic acid nano-wire array film;
Step 3: gluing-bonding-sintering-absorption;
At first at the prepared colloidal tio 2 of conductive glass surface coating step 1; Metatitanic acid nano-wire array film with step 2 gained is bonded in above the colloidal tio 2 then, obtains the laminated film of poriferous titanium dioxide nano-crystal film and nano-wire array film of titanium dioxide after drying in 200～600 ℃ of following sintering; At last laminated film is soaked in absorbing dye sensitizer in the dye sensitization agent solution, obtains final used by dye sensitization solar battery blanket type light anode.
3. the preparation method of used by dye sensitization solar battery blanket type light anode according to claim 2 is characterized in that, strong base solution described in the step 2 is NaOH or KOH solution.
4. the preparation method of used by dye sensitization solar battery blanket type light anode according to claim 2 is characterized in that, colloidal tio 2 described in the step 1 is commercially available P25 colloidal tio 2.
5. the preparation method of used by dye sensitization solar battery blanket type light anode according to claim 2, it is characterized in that, colloidal tio 2 described in the step 1 prepares voluntarily for adopting hydrothermal synthesis method, and its preparation process is as follows: adopt metatitanic acid tetrem propyl ester [Ti (i-OC
3H
7)
4], nitric acid (HNO
3), glacial acetic acid (CH
3COOH) and deionized water (H
2O) be raw material, control Ti (i-OC
3H
7)
4, HNO
3, CH
3COOH and H
2The mol ratio of O is 1: 2.8: 1: 76; At first with Ti (i-OC
3H
7)
4Be dissolved in H
2Among the O, the powerful stirring adds CH down
3COOH slowly adds HNO more while stirring
3Then reaction system is heated to 80 ℃ and change in the autoclave, hydro-thermal reaction under the pressure condition of 150～300 ℃ temperature and 0～330Mpa obtains TiO 2 sol; At last TiO 2 sol is added high molecular surfactant after vaccum dewatering is handled and regulate viscosity, obtain thick colloidal tio 2.
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| CN2010105163191A CN101950687B (en) | 2010-10-22 | 2010-10-22 | Preparation method of blanket type light anode for dye sensitized solar cell |
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| CN101950687B CN101950687B (en) | 2011-11-09 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102231332A (en) * | 2011-03-31 | 2011-11-02 | 中国科学院安徽光学精密机械研究所 | Flexible Dye-sensitized Solar Cells (DSSCs) based on titanium dioxide nanometer rod array film and preparation method thereof |
| CN102568850A (en) * | 2012-01-17 | 2012-07-11 | 上海联孚新能源科技有限公司 | Dye sensitized solar cell photoanode, cell and manufacturing method of photoanode |
| CN102674441A (en) * | 2012-04-18 | 2012-09-19 | 吉林大学 | Preparation method of controllable-structure multilayer titanate self-assembled aggregate film on titanium metal surface |
| CN103985551A (en) * | 2014-05-12 | 2014-08-13 | 电子科技大学 | Dye-sensitized solar cell photo-anode and preparing method thereof |
| CN106757141A (en) * | 2016-11-11 | 2017-05-31 | 中国科学院理化技术研究所 | A kind of method for improving silicon/metal oxide nano-wire array photoelectric chemical property |
| CN107680815A (en) * | 2017-09-18 | 2018-02-09 | 哈尔滨工业大学 | A kind of preparation method and applications of homogeneity barrier layer/skeleton titania structure |
| CN110600271A (en) * | 2019-08-30 | 2019-12-20 | 福建师范大学 | Dye-sensitized solar cell module and preparation method and application thereof |
| CN110610811A (en) * | 2019-08-30 | 2019-12-24 | 福建师范大学 | Solar cell based on dye sensitization and preparation method thereof |
| US10984959B1 (en) * | 2020-04-13 | 2021-04-20 | United Arab Emirates University | Quantum dot-sensitized solar cell and method of making the same |
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Cited By (14)
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|---|---|---|---|---|
| CN102231332A (en) * | 2011-03-31 | 2011-11-02 | 中国科学院安徽光学精密机械研究所 | Flexible Dye-sensitized Solar Cells (DSSCs) based on titanium dioxide nanometer rod array film and preparation method thereof |
| CN102231332B (en) * | 2011-03-31 | 2013-06-12 | 中国科学院安徽光学精密机械研究所 | Flexible Dye-sensitized Solar Cells (DSSCs) based on titanium dioxide nanometer rod array film and preparation method thereof |
| CN102568850A (en) * | 2012-01-17 | 2012-07-11 | 上海联孚新能源科技有限公司 | Dye sensitized solar cell photoanode, cell and manufacturing method of photoanode |
| CN102568850B (en) * | 2012-01-17 | 2015-01-07 | 上海联孚新能源科技集团有限公司 | Dye sensitized solar cell photoanode, cell and manufacturing method of photoanode |
| CN102674441A (en) * | 2012-04-18 | 2012-09-19 | 吉林大学 | Preparation method of controllable-structure multilayer titanate self-assembled aggregate film on titanium metal surface |
| CN103985551A (en) * | 2014-05-12 | 2014-08-13 | 电子科技大学 | Dye-sensitized solar cell photo-anode and preparing method thereof |
| CN106757141A (en) * | 2016-11-11 | 2017-05-31 | 中国科学院理化技术研究所 | A kind of method for improving silicon/metal oxide nano-wire array photoelectric chemical property |
| CN107680815A (en) * | 2017-09-18 | 2018-02-09 | 哈尔滨工业大学 | A kind of preparation method and applications of homogeneity barrier layer/skeleton titania structure |
| CN107680815B (en) * | 2017-09-18 | 2019-02-01 | 哈尔滨工业大学 | A kind of preparation method and applications of homogeneity barrier layer/skeleton titania structure |
| CN110600271A (en) * | 2019-08-30 | 2019-12-20 | 福建师范大学 | Dye-sensitized solar cell module and preparation method and application thereof |
| CN110610811A (en) * | 2019-08-30 | 2019-12-24 | 福建师范大学 | Solar cell based on dye sensitization and preparation method thereof |
| CN110610811B (en) * | 2019-08-30 | 2021-02-26 | 福建师范大学 | Solar cell based on dye sensitization and preparation method thereof |
| CN110600271B (en) * | 2019-08-30 | 2021-07-13 | 福建师范大学 | Dye-sensitized solar cell module and preparation method and application thereof |
| US10984959B1 (en) * | 2020-04-13 | 2021-04-20 | United Arab Emirates University | Quantum dot-sensitized solar cell and method of making the same |
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