CN103198924A - Photo-anode of dye-sensitized solar cell and preparation method thereof - Google Patents
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Abstract
The invention discloses a photo-anode of a dye-sensitized solar cell and a preparation method thereof. A porous polymer membrane is used as a primary structure template, a hydrolysable compound is used as a precursor, a segmented copolymer is used as a secondary structure directing agent, fluorine-doped tin oxide (FTO) or indium tin oxide (ITO) conducting glass is used as a substrate, and a metallic oxide porous membrane is adhered to an FTO or ITO conducting face through an alcoholysis reaction and high-temperature calcinations of the precursor. The prepared porous membrane is provided with a unique secondary structure and is suitable for the photo-anode of the dye-sensitized solar cell, and the preparation method is simple in process and environment-friendly.
Description
Technical field
The invention belongs to field of energy source materials, relate to light anode of a kind of DSSC and preparation method thereof.
Background technology
Dye-sensitized solar cells mainly is imitation photosynthesis principle; a kind of novel solar cell of developing; with respect to normally used crystal silicon solar energy battery; its main advantage is: abundant raw materials, cost is low, technology is simple relatively; in the large tracts of land suitability for industrialized production, has bigger advantage; all raw material and production technology all are nontoxic, free of contamination simultaneously, and the part material can be reclaimed fully, and the protection human environment is had great importance.Since Lausanne, SUI senior engineer (EPFL) M. in 1991
Professor leader's research group it is found that DSSC at solar energy development and the great potential aspect utilizing since the breakthrough that this technology gets on, developed countries such as Europe, the United States, day drop into the substantial contribution research and development.The critical component of this battery is semi-conducting electrode.This semi-conducting electrode generally is made up of semiconductor nanoparticle.The transmission resistance that electric charge conducts between this semiconductor nanoparticle is bigger, and this has hindered the further raising of this battery in photoelectric conversion efficiency.As a new technology that faces the future, employed nanometer porous titanium oxide active layer generally only has 5-20 μ m thick in the DSSC.In DSSC, be subjected to light activated light-sensitive coloring agent and produce supper-fast light induced electron, and electronics is injected into the conduction band of titanium oxide, and in dyestuff regenerative process subsequently, thereby photohole is conducted to the overall process that current collector is finished opto-electronic conversion through titanium oxide.In this course, the titanium oxide active layer is a kind of charge-conduction material of key, and obviously, preparing high-quality titanium oxide layer is an important directions of exploitation DSSC.
Summary of the invention
The purpose of this invention is to provide light anode of a kind of DSSC and preparation method thereof.
The light anode of solar cell provided by the invention comprises conductive coating and metal oxide porous rete from the bottom to top successively;
Wherein, the material that constitutes described metal oxide porous rete is selected from the oxide of following metallic element at least a: Ti, Zn, Sn and Nb;
The material that constitutes described conductive coating be selected from fluorine-doped tin oxide (Fluorine doped tin oxide, FTO) and indium tin metal oxide (Indium Tin Oxides, at least a in ITO).
Above-mentioned smooth anode also can be only by above-mentioned two-layer the composition.
The thickness of described metal oxide porous rete is 6-40 μ m, is specially 5 μ m, 6 μ m, 10 μ m or 5-10 μ m, 6-10 μ m or 5-6 μ m;
The diameter in hole is 2-50nm, is specially 20nm;
Porosity is 30-60%, is specially 30%, 40% or 30-40%;
The thickness of described conductive coating is 400-1000nm, is specially 600nm.
The method of the described smooth anode of preparation provided by the invention comprises the steps:
1) perforated membrane is not destroyed the surface treatment of its structure after, obtain the perforated membrane after the surface treatment;
2) mixing in ethanol carries out alcoholysis reaction with precursor compound and structure directing agent, obtains colloidal sol;
3) get part steps 2) gained colloidal sol soaking step 1) gained surface-treated perforated membrane 0.5-24 hour, the perforated membrane after obtaining soaking;
4) get part steps 2) gained colloidal sol is coated on the electro-conductive glass, obtains being coated with the electro-conductive glass of colloidal sol;
5) perforated membrane after the step 3) gained is soaked spreads on the electro-conductive glass that the step 4) gained is coated with colloidal sol, remove unnecessary colloidal sol after, room temperature leaves standstill, calcining naturally cools to room temperature, obtains described smooth anode.
In the described step 1) of said method, the material that constitutes described perforated membrane is selected from least a in polypropylene, polyethylene, polyimides and the Merlon;
The thickness of described perforated membrane is 10 μ m-60 μ m, is specially 25 μ m, 10 μ m, 10-25 μ m; The diameter in hole is 10nm-500nm, is specially 100nm; Porosity is 30-60%, is specially 40%;
Described step 1) surface-treated mode is that oxygen plasma treatment or surface chemical modification are handled;
In the described oxygen plasma treatment, power is 10-30W, is specially 18W, and the time is 10-120 second, is specially 30 seconds;
During described surface chemical modification was handled, used modifier was selected from least a in vinyltrimethoxy silane, methacryloxypropyl trimethoxy silane and the vinyltriethoxysilane; Modification time is 2-12 hour, is specially 8 hours; Temperature is 40-90 ℃, is specially 70 ℃.
Described step 2) in, precursor compound is selected from the salt of following metallic element and the ester at least a: Ti, Zn, Sn and Nb specifically are selected from least a in titanium tetrachloride, tetrabutyl titanate, phthalic acid two zinc esters, stannic acid ester and the niobates;
Described structure directing agent is block copolymer, is specially poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer F127 (EO
106PO
70EO
106) and P123 (EO
20PO
70EO
20) at least a;
The weight average molecular weight of described block copolymer is for being respectively 10500-12500g/mol and 5000-6800g/mol;
It is the P123 of 5800g/mol that described block copolymer is specially F127 or the weight average molecular weight that weight average molecular weight is 11500g/mol;
Described precursor compound, structure directing agent and consumption of ethanol are than being 1-10mL: 0.3-1.5g: 10-30mL g is specially 5mL: 0.9g: 20mL, 3mL: 0.9g: 20mL, 5mL: 1.5g: 20mL, 3-5mL: 0.9g: 20mL or 3-5mL: 0.9-1.5g: 20mL;
In the described alcoholysis reaction step, temperature is 20-80 ℃, is specially 60 ℃, and the time is 2-24 hour, is specially 12 hours.
Described step 5) leaves standstill in the step, and the time is 2-24 hour, is specially 12 hours;
In the described calcining step, the heating rate that is risen to calcining heat by room temperature is 2-4 ℃/min, is specially 4 ℃/min; Calcining heat is 380-450 ℃, is specially 450 ℃; Calcination time is 2-6 hour, is specially 2 hours; The atmosphere that is risen to calcining step and calcining and cooling step by room temperature is air atmosphere.
In addition, the light anode that the invention described above provides preparation in the solar cell application and contain the solar cell of this light anode, also belong to protection scope of the present invention.Wherein, described solar cell specifically can be DSSC, and described dyestuff is specially the N3 dyestuff.
The present invention is the primary structure template with the apertured polymeric film, be presoma with the hydrolyzable compound, being the secondary structure directed agents with the block copolymer, is substrate with FTO or ito glass, by hydrolysis and high-temperature calcination oxide porous film of adhesion metal on FTO or ITO conducting surface of presoma.Advantages such as this perforated membrane has unique secondary structure, and the particle queueing discipline has nano-pore structure, and specific surface is big, and technology is simple, and with low cost, suitable large-scale production is applicable to the preparation dye-sensitized solar cell anode.Gained titanium oxide active layer forms for the titan oxide particles unit that adapts with perforated membrane hole shape size be orientated accumulation by certain orientation, and learn by dependence test, the density size that titanium oxide layer is piled up in substrate has directly determined photoelectric conversion efficiency, primary structure template perforated membrane is more thick, the relative amount of presoma (10%-30%) is more big, the titanium oxide bulk density is more high, and corresponding photoelectric conversion efficiency is also just more high.
Description of drawings
Fig. 1 is embodiment 1 prepared photocatalytic titanium oxide anode surface SEM photo.
Fig. 2 is embodiment 2 prepared photocatalytic titanium oxide anode section S EM photos.
Fig. 3 is embodiment 3 prepared photocatalytic titanium oxide anode section S EM photos.
Fig. 4 is embodiment 4 prepared photocatalytic titanium oxide anode section S EM photos.
Fig. 5 is prepared photocatalytic titanium oxide anode section S EM photo.
Fig. 6 is prepared photocatalytic titanium oxide anode structure level.
Fig. 7 is embodiment 1 prepared photocatalytic titanium oxide anode assembling solar cell I-V curve.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can get from open commercial sources if no special instructions.
Embodiment 1
1) be that (aperture is 20nm, and porosity is 40% for the porous polypropylene film of 25 μ m with thickness; Weight average molecular weight is 100w g/mol, and available from Celgard company, production code member is Celgard
@2500) do not destroy the oxygen plasma surface treatment (power is 18W, and the time is 30 seconds) of its structure after, obtain the porous polypropylene film after the surface treatment;
This step also mode of usable surface chemical modification is handled porous polypropylene film, and concrete steps comprise: with vinyltrimethoxy silane with porous polypropylene film in 70 ℃ of immersion treatment 8 hours;
2) be the block copolymer F-127 (EO of 11500g/mol with 0.9 gram structure directing agent weight average molecular weight
106PO
70EO
106, available from BASF AG, production code member is F-127) join in the 20mL absolute ethyl alcohol, again 5mL presoma titanium tetrachloride is slowly added wherein, be sealed in 60 ℃ of heating afterwards and carried out alcoholysis reaction 4 hours, obtain colloidal sol;
3) get part steps 2) gained colloidal sol soaking step 1) gained surface-treated porous polypropylene film left standstill 4 hours, treated that perforated membrane soaks into fully, the porous polypropylene film after obtaining soaking;
4) get part steps 2) gained colloidal sol is coated on the conductive coating face of FTO electro-conductive glass that thickness is 3mm, obtains being coated with the electro-conductive glass of colloidal sol;
5) porous polypropylene film after the step 3) gained is soaked spreads on the electro-conductive glass that the step 4) gained is coated with colloidal sol, after rotation mode is removed unnecessary colloidal sol, after room temperature leaves standstill 12 hours, programming rate with 4 ℃/min in tube furnace was warming up to 450 ℃ of insulation calcinings after 2 hours, naturally cool to room temperature, intensification, whole calcination process all carry out in air atmosphere, naturally cool to room temperature, obtain smooth anode provided by the invention.
This light anode is from the bottom to top successively by FTO electro-conductive glass and TiO
2The porous rete is formed; TiO wherein
2The thickness of porous rete is 10 μ m, and the diameter in hole is 20nm, and porosity is 30%; Oxidation titanium film pattern such as Fig. 1.The thickness of FTO electro-conductive glass is 3mm, and wherein the thickness of FTO conductive coating is 600nm.
Fig. 5 is prepared photocatalytic titanium oxide anode section S EM photo.Layer of structure can be observed by ESEM, and as shown in Figure 6, used ESEM is JSM 6700F type field emission scanning electron microscope.
With this light anode assembling solar battery as follows:
At first, the light anode is placed on soaked overnight in the solution of N3 (ruthenium complex) dyestuff, the zone from three limits of the oxidation titanium film of light anode to corresponding basal edge is cemented covering with adhesive tape, reserve a fringe region and connect circuit and use; Secondly, drip electrolyte at oxidation titanium film, cover electrode (Pt electrode) and fixing, namely obtain fuel cell.
The preparation method of Pt electrode is: with chloroplatinic acid (H
2PtCl
66H
2O) aqueous isopropanol (mass percentage concentration is 0.5%) drips on FTO electro-conductive glass conducting surface, and 400 ℃ of heat treatment is 0.5 hour in tube furnace, reprocessing 5 times.Be 11nm to electrode Pt metal layer thickness.
The ethanolic solution concentration of N3 dyestuff is 3 * 10
-4Mol/L.
After tested, the short-circuit current density of this solar cell is 9.17mA/cm
2, open circuit voltage is 0.77V, and fill factor, curve factor is 0.47, and photoelectric conversion rate is 3.35%.I-V curve such as Fig. 7.Battery is at room temperature tested by ORIEL81193 type solar simulator (light source is xenon lamp) and KEITHLEY4200 type semiconducting behavior tester.The light intensity of light source is calibrated by ORIEL standard silicon battery, and intensity of illumination is 100mW/cm
2, the effective area of battery is 0.25cm
2
As from the foregoing, the DSSC that this method prepares the assembling of light anode has higher energy conversion efficiency, can be applied to fuel cell field.
According to the step of embodiment 1, only the volumetric usage with titanium tetrachloride replaces with 3mL, obtains smooth anode provided by the invention.
This light anode is by FTO electro-conductive glass and TiO
2The porous rete is formed; TiO wherein
2The thickness of porous rete is 6 μ m, and the diameter in hole is 20nm, and porosity is 40%; The thickness of FTO electro-conductive glass is 3mm, and wherein the thickness of FTO conductive coating is 600nm.Oxidation titanium film pattern such as Fig. 2.
Method according to embodiment 1 is assembled into solar cell with gained light anode, and its performance is as follows: short-circuit current density is 5.32mA/cm
2, open circuit voltage is 0.79V, and fill factor, curve factor is 0.40, and photoelectric conversion rate is 2.39%.
As from the foregoing, the consumption that reduces the titanium source causes the thickness of film and tightness to reduce, and energy conversion efficiency reduces.
Embodiment 3
According to the step of embodiment 1, only titanium tetrachloride is replaced with phthalic acid two zinc esters, obtain smooth anode provided by the invention.
This light anode is made up of FTO electro-conductive glass and ZnO porous rete; Wherein the thickness of ZnO porous rete is 10 μ m, and the diameter in hole is 20nm, and porosity is 30%; The thickness of FTO conductive coating is 600nm.The thickness of FTO electro-conductive glass is 3mm, and wherein the thickness of FTO conductive coating is 600nm.Oxidation titanium film pattern such as Fig. 3.
Method according to embodiment 1 is assembled into solar cell with gained light anode, and its performance is as follows: short-circuit current density is 4.67mA/cm
2, open circuit voltage is 0.80V, and fill factor, curve factor is 0.49, and photoelectric conversion rate is 2.40%.
As from the foregoing, this method also is applicable to zinc oxide to be light anode preparation DSSC.
Step according to embodiment 1 only replaces with tetrabutyl titanate with titanium tetrachloride, obtains smooth anode provided by the invention.
This light anode is by FTO electro-conductive glass and TiO
2The porous rete is formed; TiO wherein
2The thickness of porous rete is 10 μ m, and the diameter in hole is 20nm, and porosity is 30%; The thickness of FTO conductive coating is 600nm.The thickness of FTO electro-conductive glass is 3mm, and wherein the thickness of FTO conductive coating is 600nm.Oxidation titanium film pattern such as Fig. 4.
Method according to embodiment 1 is assembled into solar cell with gained light anode, and its performance is as follows: short-circuit current density is 6.26mA/cm
2, open circuit voltage is 0.80V, and fill factor, curve factor is 0.47, and photoelectric conversion rate is 3.16%.
As from the foregoing, by this method, adopt the different titanium sources all can be for the preparation of the light anode of DSSC.
Embodiment 5
According to the step of embodiment 1, only the thickness with porous polypropylene film replaces with 10 μ m, obtains smooth anode provided by the invention.
This light anode is by FTO electro-conductive glass and TiO
2The porous rete is formed; TiO wherein
2The thickness of porous rete is 6 μ m, and the diameter in hole is 20nm, and porosity is 30%; The thickness of FTO electro-conductive glass is 3mm, and wherein the thickness of FTO conductive coating is 600nm.
Method according to embodiment 1 is assembled into solar cell with gained light anode, and its performance is as follows: short-circuit current density is 6.17mA/cm
2, open circuit voltage is 0.77V, and fill factor, curve factor is 0.44, and photoelectric conversion rate is 2.35%.
As from the foregoing, the less thick of template film causes the oxidation titanium film less thick, and then the energy conversion efficiency of battery is reduced.
Embodiment 6
According to the step of embodiment 1, only the volumetric usage with titanium tetrachloride replaces with 3mL, and the thickness of porous polypropylene film replaces with 10 μ m, obtains smooth anode provided by the invention.
This light anode is by FTO electro-conductive glass and TiO
2The porous rete is formed; TiO wherein
2The thickness of porous rete is 5 μ m, and the diameter in hole is 20nm, and porosity is 40%; The thickness of FTO electro-conductive glass is 3mm, and wherein the thickness of FTO conductive coating is 600nm.
Method according to embodiment 1 is assembled into solar cell with gained light anode, and its performance is as follows: short-circuit current density is 4.32mA/cm
2, open circuit voltage is 0.80V, and fill factor, curve factor is 0.43, and photoelectric conversion rate is 2.19%.
As from the foregoing, reduce titanium source consumption and use thinner template film can cause prepared oxidation titanium film thickness and tightness significantly to reduce, thereby cause the efficient of battery lower.
Embodiment 7
According to the step of embodiment 1, only titanium tetrachloride is replaced with phthalic acid two zinc esters, the thickness of porous polypropylene film replaces with 10 μ m, obtains smooth anode provided by the invention.
This light anode is by FTO electro-conductive glass and TiO
2The porous rete is formed; TiO wherein
2The thickness of porous rete is 6 μ m, and the diameter in hole is 20nm, and porosity is 30%; The thickness of FTO electro-conductive glass is 3mm, and wherein the thickness of FTO conductive coating is 600nm.
Method according to embodiment 1 is assembled into solar cell with gained light anode, and its performance is as follows: short-circuit current density is 4.48mA/cm
2, open circuit voltage is 0.79V, and fill factor, curve factor is 0.41, and photoelectric conversion rate is 2.13%.
As from the foregoing, as long as the attenuation of employed template film, no matter the oxide kind how, the efficient of prepared battery all can reduce.
Step according to embodiment 1 only replaces with tetrabutyl titanate with titanium tetrachloride, and the thickness of porous polypropylene film replaces with 10 μ m, obtains smooth anode provided by the invention.
This light anode is by FTO electro-conductive glass and TiO
2The porous rete is formed; TiO wherein
2The thickness of porous rete is 6 μ m, and the diameter in hole is 20nm, and porosity is 30%; The thickness of FTO electro-conductive glass is 3mm, and wherein the thickness of FTO conductive coating is 600nm.
Method according to embodiment 1 is assembled into solar cell with gained light anode, and its performance is as follows: short-circuit current density is 6.01mA/cm
2, open circuit voltage is 0.78V, and fill factor, curve factor is 0.48, and photoelectric conversion rate is 2.56%.
As from the foregoing, under the same conditions, titanium source category difference, battery efficiency also is not quite similar.
Embodiment 9
According to the step of embodiment 1, only the consumption with block copolymer F-127 replaces with 1.5g, obtains smooth anode provided by the invention.
This light anode is by FTO electro-conductive glass and TiO
2The porous rete is formed; TiO wherein
2The thickness of porous rete is 10 μ m, and the diameter in hole is 20nm, and porosity is 30%; The thickness of FTO electro-conductive glass is 3mm, and wherein the thickness of FTO conductive coating is 600nm.
Method according to embodiment 1 is assembled into solar cell with gained light anode, and its performance is as follows: short-circuit current density is 7.36mA/cm
2, open circuit voltage is 0.79V, and fill factor, curve factor is 0.43, and photoelectric conversion rate is 3.09%.
As from the foregoing, the consumption of structure directing agent also has certain influence to battery efficiency.
Claims (10)
1. the light anode of a solar cell comprises by the electro-conductive glass that contains conductive coating and the metal oxide porous rete that is positioned on the described conductive coating;
Wherein, the material that constitutes described metal oxide porous rete is selected from the oxide of following metallic element at least a: Ti, Zn, Sn and Nb;
The material that constitutes described conductive coating is at least a in fluorine-doped tin oxide and the indium tin metal oxide.
2. smooth anode according to claim 1 is characterized in that: described smooth anode is made up of the electro-conductive glass that contains described conductive coating and the metal oxide porous rete that is positioned on the described conductive coating.
3. smooth anode according to claim 1 and 2, it is characterized in that: the thickness of described electro-conductive glass is 2-4mm; Or,
The thickness of described conductive coating is 400nm-1000nm, is specially 600nm; Or,
The thickness of described metal oxide porous rete is 6-40 μ m, is specially 10 μ m; Or,
The diameter in hole is 2-200nm, is specially 20nm; Or,
Porosity is 30%-60%, is specially 40%.
4. a method for preparing the arbitrary described smooth anode of claim 1-3 comprises the steps:
1) perforated membrane is not destroyed the surface treatment of its structure after, obtain the perforated membrane after the surface treatment;
2) mixing in ethanol carries out alcoholysis reaction with precursor compound and structure directing agent, obtains colloidal sol;
3) get part steps 2) gained colloidal sol soaking step 1) gained surface-treated perforated membrane 0.5-24 hour, the perforated membrane after obtaining soaking;
4) get part steps 2) gained colloidal sol is coated on the described electro-conductive glass, obtains being coated with the electro-conductive glass of colloidal sol;
5) perforated membrane after the step 3) gained is soaked spreads on the electro-conductive glass that the step 4) gained is coated with colloidal sol, remove unnecessary colloidal sol after, room temperature leaves standstill, calcining naturally cools to room temperature, obtains described smooth anode.
5. method according to claim 4 is characterized in that: in the described step 1), the material that constitutes described perforated membrane is selected from least a in polypropylene, polyethylene, polyimides and the Merlon; Or,
The thickness of described perforated membrane is 10 μ m-60 μ m; The diameter in hole is 10nm-500nm, is specially 100nm; Porosity is 20-60%, is specially 40%; Or,
Described step 1) surface-treated mode is that oxygen plasma treatment or surface chemical modification are handled; Or,
In the described oxygen plasma treatment, power is 10-30W, is specially 18W, and the time is 10-120 second, is specially 30 seconds; Or,
During described surface chemical modification was handled, used modifier was selected from least a in vinyltrimethoxy silane, methacryloxypropyl trimethoxy silane and the vinyltriethoxysilane; Modification time is 2-12 hour, is specially 8 hours; Temperature is 40-90 ℃, is specially 70 ℃.
6. according to claim 4 or 5 described methods, it is characterized in that: described step 2), precursor compound is selected from the salt of following metallic element and the ester at least a: Ti, Zn, Sn and Nb specifically are selected from least a in titanium tetrachloride, tetrabutyl titanate, phthalic acid two zinc esters, stannic acid ester and the niobates; Or,
Described structure directing agent is block copolymer, is specially poly(ethylene oxide)-PPOX-poly(ethylene oxide) triblock copolymer EO
106PO
70EO
106And EO
20PO
70EO
20In at least a; Or,
The weight average molecular weight of described block copolymer is respectively 10500-12500g/mol and 5000-6800g/mol; Or,
Described block copolymer is specially the EO that weight average molecular weight is 11500g/mol
106PO
70EO
106Or weight average molecular weight is the EO of 5800g/mol
20PO
70EO
20Or,
Described precursor compound, structure directing agent and consumption of ethanol are than being 1-10mL: 0.3-1.5g: 10-30mL; Or,
In the described alcoholysis reaction step, temperature is 20-80 ℃, is specially 60 ℃, and the time is 2-12 hour, is specially 12 hours.
7. according to the arbitrary described method of claim 4-6, it is characterized in that: described step 5) leaves standstill in the step, and the time is 2-24 hour; Or,
In the described calcining step, the heating rate that is risen to calcining heat by room temperature is 2-4 ℃/min, is specially 4 ℃/min; Or,
Calcining heat is 380-450 ℃, is specially 450 ℃; Or,
Calcination time is 2-6 hour, is specially 2 hours; Or,
The atmosphere that is risen to calcining step and calcining and cooling step by room temperature is air atmosphere.
8. the application of the arbitrary described smooth anode of claim 1-3 in the preparation solar cell.
9. the solar cell that contains the arbitrary described smooth anode of claim 1-3.
10. the described solar cell of application according to claim 8 or claim 9, it is characterized in that: described solar cell is DSSC; Or,
Described dyestuff is specially the N3 dyestuff.
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| CN103700505A (en) * | 2013-12-30 | 2014-04-02 | 中国科学院上海硅酸盐研究所 | Method for rapidly sintering large-area photoanode of dye-sensitized solar cell (DSSC) |
| CN103700505B (en) * | 2013-12-30 | 2016-04-13 | 中国科学院上海硅酸盐研究所 | The method of Fast Sintering large-area dye-sensitized solar battery photo-anode |
| CN105742506A (en) * | 2016-02-29 | 2016-07-06 | 苏州大学 | Organic-inorganic hybrid photoelectrochemical anode electrode and preparation method thereof |
| CN105742506B (en) * | 2016-02-29 | 2019-01-01 | 苏州大学 | A kind of hybrid inorganic-organic optical electro-chemistry anode electrode and preparation method thereof |
| CN106731886A (en) * | 2016-12-27 | 2017-05-31 | 深圳市星源材质科技股份有限公司 | A kind of preparation method of composite mesoporous film |
| CN106731886B (en) * | 2016-12-27 | 2019-12-24 | 深圳市星源材质科技股份有限公司 | Preparation method of mesoporous composite membrane |
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