CN100423314C - Dye sensitization nanocrystalline solar battery based on dendroid compounds and its preparing method - Google Patents
Dye sensitization nanocrystalline solar battery based on dendroid compounds and its preparing method Download PDFInfo
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- CN100423314C CN100423314C CNB2005100293304A CN200510029330A CN100423314C CN 100423314 C CN100423314 C CN 100423314C CN B2005100293304 A CNB2005100293304 A CN B2005100293304A CN 200510029330 A CN200510029330 A CN 200510029330A CN 100423314 C CN100423314 C CN 100423314C
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Abstract
The present invention belongs to the technical field of solar batteries, more specifically a full-solid electrolyte dye sensitized nanometer-crystal solar battery which is filled with a dendritic compound and a preparation method thereof. In the solar battery, the surface of large-energy-gap semiconductor nanometer crystal coating which is capable of adsorbing photosensitizer is assembled with a full-solid electrolyte instead of a liquid electrolyte, and the electrolyte is filled with the dendritic compound. The present invention can solve the problem of solution leakage and volatilization, and can obviously prolong the service life of the solar battery.
Description
Technical field
The invention belongs to technical field of solar batteries, be specifically related to a kind of dye sensitized nano crystal salar battery and preparation method thereof.
Background technology
Along with the develop rapidly of modern science and technology, energy and environment have become 21 century and have pressed for one of key issue of solution.Solar energy is inexhaustible green resource, is the optimal path that addresses this problem, so countries in the world competitively carry out the research that how to utilize solar energy one after another, and wherein solar cell is one of wherein important branch.The application of solar cell at present mainly concentrates on the monocrystalline silicon and the non-silicon solar cell of based semiconductor photovoltaic effect, though its photoelectric conversion efficiency height, complex process, cost an arm and a leg, the material requirements harshness, thereby be difficult to popularize.Nineteen nineties, the M. of Lausanne, SUI university
Professor has worked out dye sensitized nano crystal salar battery (referring to International Patent Application WO 91/16719), this dye sensitized nano crystal salar battery can overcome the shortcoming of silicon solar cell, have advantages such as manufacture craft is simple, material purity is less demanding, cheap, become the research focus in this field.
It is work electrode that dye sensitized nano crystal salar battery adopts the nanometer crystal film of the wide bandgap semiconductor of surface adsorption sensitising agent, because nanometer crystal film has very large specific area, can adsorb a large amount of sensitising agents, thereby can effectively absorb sunlight.The operation principle of dye sensitized nano crystal salar battery: when dyestuff absorbs sunlight, electronics is from the ground state transition to excitation state, the electronics of excitation state is transferred to rapidly in the semi-conductive conduction band, and the hole is stayed in the dyestuff, electronics is transferred to electrode through external circuit with after the Nano semiconductor network diffuses to conductive substrates, and the dyestuff of oxidation state is reduced the electrolyte reduction of attitude, the electrolyte of oxidation state is reduced in that electrode is accepted electronics, thereby finishes the transportation of electronics.
At present, the electrolyte of dye sensitized nano crystal salar battery mainly adopts and contains I
3 -/ I
2The acetonitrile solution of oxidation-reduction pair, but there is the problem of solvent evaporates and leakage in liquid electrolyte.In order to overcome these shortcomings, develop into the quasi-solid electrolyte that contains some gelatinizing agents gradually, improved the stability of battery to a certain extent.
In order to solve the stability of solar cell fully, all solid state electrolyte is best selection.Solid electrolyte mainly adopts solid polymer, p-type inorganic semiconductor, organic hole transferring material etc. at present, but the ionic conductivity of all solid state electrolyte sharply descends, effect is unsatisfactory, therefore, the efficient that how to improve the dye sensitized nano crystal salar battery of solid electrolyte becomes the important development direction of dye sensitized nano crystal salar battery.
Summary of the invention
The object of the present invention is to provide dye sensitized nano crystal salar battery of a kind of battery efficiency height, long service life and preparation method thereof.
The dye sensitized nano crystal salar battery that the present invention proposes, its all solid state electrolyte is assembled on the surface of the wide bandgap semiconductor nanometer crystal film that is adsorbed with photosensitizer, replace conventional liquid electrolyte, and form sandwich shape with the electro-conductive glass that is coated with platinum layer, wherein the dye sensitized nano crystal film is a work electrode, the electro-conductive glass of platinum plating layer is to electrode, and carries out simplified package with heat-seal adhesive, and its structural representation as shown in Figure 1.Wherein, adding in all solid state electrolyte has dendrimer, and the mass content of dendrimer in all solid state electrolyte is 1-10%.
Among the present invention, described dendrimer can be selected a kind of of poly-benzylic type of 1-3 generation, polyamide type, polypropylene imines type etc. for use, and its structure as shown in Figure 2.
Wide bandgap semiconductor nanometer crystal film of the present invention adopts the titanium dioxide nanocrystalline film, photosensitizer adopts cis-two thiocyanate radical-two (4,4 '-dicarboxylic acids-2,2 ' bipyridine) closes ruthenium cis-dithiocyanato bis (4,4 ' dicarboxy-2,2 '-bipyridine) ruthenium (being called for short the N3 dyestuff) and cis-two thiocyanate radical-4,4 '-dicarboxylic acids-2,2 ' bipyridine-4,4 '-dinonyl-2,2 ' bipyridine closes ruthenium cis-dithiocyanato 4,4 '-dicarboxy-2,2 '-bipyridine-4,4 '-dinonyl-2,2 '-bipyridineruthenium (being called for short the Z907 dyestuff)
Among the present invention, ionic liquid is selected from 1, and the salt compounded of iodine of 2-dialkylimidazolium, alkyl are selected from methyl, ethyl until octadecyl.
Among the present invention, above-mentioned electro-conductive glass can adopt the tin ash electro-conductive glass of mixing fluorine.
The invention allows for the preparation method of dye sensitized nano crystal salar battery, its step is as follows: assemble all solid state electrolyte on the surface of the wide bandgap semiconductor nanometer crystal film that passes through dye sensitization, electro-conductive glass with platinum plating is placed on the semiconductor nano epitaxial of dye sensitization then, promptly constitute the sandwich type dye sensitized nano crystal salar battery, and encapsulate with heat-seal adhesive.
In the said method, the wide bandgap semiconductor nanometer crystal film adopts the nano titanium oxide epitaxial.
In the said method, the preparation method of semiconductor nano epitaxial is as follows: with granularity is that the colloidal tio 2 of 10-100 nanometer is coated on and forms broad stopband nano titanium oxide epitaxial on the transparent conductive substrate, 200-600 ℃ of following roasting 15 minutes to 12 hours, cooling back repetitive operation was until the broad stopband nano titanium oxide epitaxial that obtains the 1-50 micron.Wherein transparent conductive substrate adopts the tin ash electro-conductive glass of mixing fluorine.
In the said method, dye sensitization is as follows: broad stopband nano titanium oxide epitaxial is put into baking oven heated 10-120 minute down in 100-250 ℃, being immersed in concentration when being cooled to 25-100 ℃ is 10
-5-10
-3Sensitization in 2-48 hour in the N3 of mol or the Z907 dyestuff.
In the said method, the step of assembling all solid state electrolyte is as follows: with electrolyte constituent I
2, LiI, 4-tert .-butylpyridine be dissolved into 1 respectively, in the 3-dialkylimidazolium salt compounded of iodine, its concentration is respectively: I
2Concentration be the 0.05-0.5 mol, the concentration of LiI is the 0.05-0.5 mol, the concentration of 4-tert .-butylpyridine is the 0.1-1.0 mol, to be mixed evenly after, add dendrimer, electrolyte solidifies rapidly, and wherein the mass content of dendrimer is 1-10%.
In the said method, described 1, the alkyl of 3-dialkylimidazolium salt compounded of iodine is that methyl, ethyl are until octadecyl etc.
In the said method, described dendrimer is selected from poly-benzylic ether type of 1-3 generation, polyamide type, polypropylene imines type etc.
The Optical Electro-Chemistry of dye sensitized nano crystal salar battery of the present invention is measured according to traditional three-electrode system and is measured, radiation source be 1000W solar simulator (1.5AM) (Oriel, USA).Photoelectric current and photovoltage output are measured by Keithley2400 digital source table (U.S. Keithley company).
The dye sensitized nano crystal salar battery that the present invention proposes, its all solid state electrolyte uses dendrimer as packing material, can avoid the leakage and the volatilization of solvent in the liquid electrolyte, obviously improve dye sensitized nano crystal salar battery conversion efficiency, increase the service life.
Description of drawings
Fig. 1 dye sensitized nano crystal salar battery structural representation of the present invention.
The structural representation of Fig. 2 dendrimer.
Fig. 3 is based on the photoelectric current-photovoltage curve of the dye sensitized nano crystal salar battery of all solid state electrolyte of 10% generation polypropylene imines type dendrimer.
Fig. 4 based on 3% two generation polypropylene imines type dendrimer the photoelectric current-photovoltage curve of dye sensitized nano crystal salar battery of all solid state electrolyte.
Fig. 5 is based on the photoelectric current-photovoltage curve of the dye sensitized nano crystal salar battery of all solid state electrolyte of three generations's polypropylene imines type dendrimer of 1%.
Fig. 6 is based on the photoelectric current-photovoltage curve of the dye sensitized nano crystal salar battery of the solid electrolyte dendrimer of 10% generation polyamide type.
Fig. 7 based on 3% two generation polyamide type dendrimer the photoelectric current-photovoltage curve of dye sensitized nano crystal salar battery of all solid state electrolyte.
Fig. 8 is based on the photoelectric current-photovoltage curve of the dye sensitized nano crystal salar battery of all solid state electrolyte of three generations's polyamide type dendrimer of 1%.
Fig. 9 is based on the photoelectric current-photovoltage curve of dye sensitized nano crystal salar battery of all solid state electrolyte of poly-benzylic ether type dendrimer of two generations of 3%.
Number in the figure: 1 is electro-conductive glass, and 2 is the semiconductor nano epitaxial, and 3 is photosensitizer, and 4 is solid electrolyte, and 5 is platinum layer, and 6 is electro-conductive glass.
Embodiment
Embodiment 1: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol N3 dyestuff.Drip 0.1 milliliter and contain 0.05 mol I
20.5 mol 4-tert .-butylpyridine, 0.5 mol LiI, 1-methyl-3-propyl group-iodonium imidazolide salts the solid electrolyte of 10% generation polypropylene imines type dendrimer, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure with clamp.At 100mW/cm
2White light under record open circuit photovoltage 569mV, the short-circuit photocurrent 2.8mA/cm of electrode
2, fill factor, curve factor 0.64, energy conversion efficiency 1.0%.
Embodiment 2: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol N3 dyestuff.Drip 0.1 milliliter and contain 0.5 mol I
20.5 mol 4-tert .-butylpyridine, 0.05 mol LiI, 3% two generation polypropylene imines type dendrimer 1-methyl-3-propyl group-iodonium imidazolide salts solid electrolyte, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure after encapsulating with heat-seal adhesive.At 100mW/cm
2White light under record open circuit photovoltage 589mV, the short-circuit photocurrent 4.6mA/cm of electrode
2, fill factor, curve factor 0.51, energy conversion efficiency 1.8%.
Embodiment 3: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol N3 dyestuff.Drip 0.1 milliliter and contain 0.1 mol I
21.0 mol 4-tert .-butylpyridine, 0.2 mol LiI, 1-methyl-3-propyl group-iodonium imidazolide salts the solid electrolyte of three generations's polypropylene imines type dendrimer of 1%, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure after encapsulating with heat-seal adhesive.At 100mW/cm
2White light under record open circuit photovoltage 468mV, the short-circuit photocurrent 3.0mA/cm of electrode
2, fill factor, curve factor 0.42, energy conversion efficiency 0.59%.
Embodiment 4: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol Z907 dyestuff.Drip 0.1 milliliter and contain 0.1 mol I
20.1 mol 4-tert .-butylpyridine, 0.1 mol LiI, 1-methyl-3-hexyl-iodonium imidazolide salts the solid electrolyte of 1% generation polyamide type dendrimer, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure after encapsulating with heat-seal adhesive.At 100mW/cm
2White light under record open circuit photovoltage 569mV, the short-circuit photocurrent 2.5mA/cm of electrode
2, fill factor, curve factor 0.59, energy conversion efficiency 0.83%.
Embodiment 5: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol Z907 dyestuff.Drip 0.1 milliliter and contain 0.1 mol I
20.5 mol 4-tert .-butylpyridine, 0.4 mol LiI, 3% two generation polyamide type dendrimer 1-methyl-3-hexyl-iodonium imidazolide salts solid electrolyte, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure after encapsulating with heat-seal adhesive.At 100mW/cm
2White light under record open circuit photovoltage 618mV, the short-circuit photocurrent 3.4mA/cm of electrode
2, fill factor, curve factor 0.65, energy conversion efficiency 1.35%.
Embodiment 6: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol Z907 dyestuff.Drip 0.1 milliliter and contain 0.1 mol I
20.5 mol 4-tert .-butylpyridine, 0.5 mol LiI, 1-methyl-3-octadecyl-iodonium imidazolide salts the solid electrolyte of three generations's polyamide type dendrimer of 1%, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure after encapsulating with heat-seal adhesive.At 100mW/cm
2White light under record open circuit photovoltage 483mV, the short-circuit photocurrent 3.0mA/cm of electrode
2, fill factor, curve factor 0.41, energy conversion efficiency 0.59%.
Embodiment 7: with a titanium dioxide nanocrystalline membrane electrode 5 * 10
-4Soak sensitization in 24 hours in the ethanolic solution of mol N3 dyestuff.Drip 0.1 milliliter and contain 0.1 mol I
20.5 mol 4-tert .-butylpyridine, 0.08 mol LiI, in 3% two generations, gathered the 1-methyl-3-propyl group-iodonium imidazolide salts solid electrolyte of benzylic ether type dendrimer, then the ito glass of a slice platinum plating is placed on dye sensitization the nano titanium oxide epitaxial on, measure after encapsulating with heat-seal adhesive.At 100mW/cm
2White light under, open circuit photovoltage 429mV, short-circuit photocurrent 1.1mA/cm
2, fill factor, curve factor 0.55, energy conversion efficiency 0.20%.
The photoelectric current of the solar cell of the foregoing description 1-7-photovoltage curve is seen Fig. 3-shown in Figure 9 respectively.
Claims (8)
1. a dye sensitized nano crystal salar battery is characterized in that assembling all solid state electrolyte on the surface of the wide bandgap semiconductor nanometer crystal film that adsorbs photosensitizer, and forms sandwich shape with the electro-conductive glass that is coated with platinum layer; Wherein, the dye sensitized nano crystal film is a work electrode, and the electro-conductive glass of platinum plating layer is to electrode; All solid state electrolyte is packing material with the dendrimer, and the mass content of packing material is the 1-10% of all solid state electrolyte, and this dendrimer is selected from a kind of of the 1-3 poly-benzylic ether type in generation, polyamide type, polypropylene imines type.
2. dye sensitized nano crystal salar battery according to claim 1 is characterized in that the wide bandgap semiconductor nanometer crystal film is the titanium dioxide nanocrystalline film.
3. dye sensitized nano crystal salar battery according to claim 1 is characterized in that said photosensitizer is N3 or Z907 dyestuff.
4. dye sensitized nano crystal salar battery according to claim 1 is characterized in that ionic liquid is selected from 1, and the salt compounded of iodine of 2-dialkylimidazolium, alkyl are selected from methyl, ethyl until octadecyl.
5. preparation method as one of claim 1-4 described dye sensitized nano crystal salar battery, it is characterized in that on the surface of the wide bandgap semiconductor nanometer crystal film that passes through dye sensitization, assembling all solid state electrolyte, electro-conductive glass with platinum plating is placed on the semiconductor nano epitaxial of dye sensitization then, promptly constitute the sandwich type dye sensitized nano crystal salar battery, and encapsulate with heat-seal adhesive.
6. the preparation method of dye sensitized nano crystal salar battery according to claim 5 is characterized in that the electrolyte constituent of assembling all solid state electrolyte is: I
2Concentration be the 0.05-0.5 mol, the concentration of LiI is the 0.1-2.0 mol, the concentration of 4-tert .-butylpyridine is the 0.1-1.0 mol, solvent is 1,3-dialkylimidazolium salt compounded of iodine, to be mixed evenly after, add dendrimer, electrolyte solidifies rapidly, and wherein the mass content of dendrimer is 1-10%.
7. the preparation method of dye sensitized nano crystal salar battery according to claim 5, the preparation process that it is characterized in that the semiconductor nano epitaxial is as follows: with granularity is that the colloidal tio 2 of 1-50 nanometer is coated on the transparent conductive substrate, form broad stopband nano titanium oxide epitaxial, 200-600 ℃ of following roasting 15 minutes to 12 hours, cooling back repetitive operation was until the broad stopband nano titanium oxide epitaxial that obtains the 1-50 micron.
8. the preparation method of dye sensitized nano crystal salar battery according to claim 5, the sensitization step that it is characterized in that nanometer crystal film is: broad stopband nano titanium oxide epitaxial is put into baking oven heated 10-120 minute down in 100-250 ℃, being immersed in concentration when being cooled to 25-100 ℃ is 10
-5-10
-3Sensitization in 2-48 hour in the N3 of mol or the Z907 dyestuff.
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| CN101901692B (en) * | 2010-04-21 | 2012-05-30 | 苏州大学 | Solar cell gel electrolyte and preparation method and application thereof |
| CN106549187B (en) * | 2016-10-27 | 2018-11-02 | 浙江大学 | A kind of dielectric film and its preparation method and application containing amphoteric ion full solid state polymer |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1464002A (en) * | 2002-06-12 | 2003-12-31 | 中国科学院化学研究所 | Comb shaped polysiloxane and solid electrolyte produced therefrom and process for preparing the same |
| JP2004335366A (en) * | 2003-05-09 | 2004-11-25 | Sharp Corp | Dye-sensitized solar cell |
| CN1564327A (en) * | 2004-04-22 | 2005-01-12 | 复旦大学 | Solar cell based on polymer doped quasi-solid state electrolyte material and its prepn. method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1464002A (en) * | 2002-06-12 | 2003-12-31 | 中国科学院化学研究所 | Comb shaped polysiloxane and solid electrolyte produced therefrom and process for preparing the same |
| JP2004335366A (en) * | 2003-05-09 | 2004-11-25 | Sharp Corp | Dye-sensitized solar cell |
| CN1564327A (en) * | 2004-04-22 | 2005-01-12 | 复旦大学 | Solar cell based on polymer doped quasi-solid state electrolyte material and its prepn. method |
Non-Patent Citations (2)
| Title |
|---|
| 科学通报. 张昌能，王淼，周晓文，林原，万世璧，李学萍，肖绪瑞，岑况，1241-1243. 2004 |
| 科学通报. 张昌能，王淼，周晓文，林原，万世璧，李学萍，肖绪瑞，岑况，1241-1243. 2004 * |
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