CN104240957A - Modification method of photo-anode of dye-sensitized solar cell - Google Patents

Modification method of photo-anode of dye-sensitized solar cell Download PDF

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CN104240957A
CN104240957A CN201410474338.0A CN201410474338A CN104240957A CN 104240957 A CN104240957 A CN 104240957A CN 201410474338 A CN201410474338 A CN 201410474338A CN 104240957 A CN104240957 A CN 104240957A
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titanium dioxide
anode
light anode
dye
solution
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施利毅
袁帅
侯睿恩
赵尹
王竹仪
张美红
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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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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Abstract

The invention discloses a modification method of the photo-anode of a dye-sensitized solar cell. The modification method comprises the steps that an M metal salt ionic compound is added into a prepared 40 mM TiCl4 solution, and a photo-anode modification solution is prepared at the indoor temperature according to the ion mole ratio that M: Ti=0.25%-2%; a titanium dioxide porous film calcined at the temperature of 500 DEG C is placed into the prepared photo-anode modification solution in a standing mode, heat of the mixture is preserved for 30 min at the temperature of 70 DEG C, the mixture is washed by deionized water and calcined for 30 min at the temperature of 500 DEG C, and the modified titanium dioxide porous film is obtained; the modified titanium dioxide porous film is soaked in N719 dye, taken out after standing of 24 h, cleaned by ethyl alcohol and blow-dried by cold air, and the photo-anode coated with the titanium dioxide porous film and modified by an M metal ion doping barrier layer is obtained. By means of the modification method, the photoelectric performance of the dye-sensitized solar cell can be greatly improved.

Description

The method of modifying of dye-sensitized solar cell anode
Technical field
The present invention relates to a kind of preparation method of DSSC, particularly relate to a kind of processing method of light anode of DSSC, be applied to and improve DSSC photoelectric properties technical field.
Background technology
Along with people are to the growing interest of environmental problem, vast researcher is devoted to find continuable clean energy resource, starts to pay close attention to Hydrogen Energy thereupon, water energy, wind energy, solar energy, and solar energy enjoys favor as a kind of inexhaustible energy.From first generation monocrystaline silicon solar cell, to the thin-film solar cells of the second generation, arrive novel third generation solar cell again, area of solar cell is also experiencing innovation, and as the DSSC of one of third generation solar cell because of its environmental friendliness, cost is low, and manufacture craft simply becomes the favorite in this field.Reported at present the most high conversion efficiency about 13% of the traditional DSSC obtained in the lab, distance commercial application also has larger gap.
Following step is related generally in DSSC:
1. be adsorbed on exciting of the dyestuff of semiconductor material surface; 2. excitation electron injects the conduction band of semi-conducting material and is transmitted to electro-conductive glass thereupon; 3. the dyestuff after exciting and the dyestuff of oxidation state are reduced by oxidation-reduction pair in electrolyte with continuous excitation electron; 4. the oxidation-reduction pair in oxidized electrolyte is reduced by the Pt of electrode to reach the effect recycled.The generation of other process can be there is in these processes, if the electronics being such as injected into semi-conducting material conduction in time will with the dyestuff generation compound of the oxidation-reduction pair in electrolyte or oxidation state, if the compound of this part electronics effectively can be reduced, the short circuit current of DSSC and open circuit voltage will all increase, thus photoelectric conversion efficiency will improve.
Over nearly 20 years, vast researchers are devoted to study the method improving photoelectric conversion efficiency in all its bearings, in suppression electron recombination, mainly contain by the top layer coated insulation material at semi-conducting material as returned electronics at titania surface coating zinc oxide to reduce thus improve DSSC performance (Solid-State Electronics 2013,87,8 – 103).For another example at the coated Al of titania surface 2o 3to suppress electron recombination (Journal of Power Sources 2010,195(15), 5138 – 5143).But shortcoming is coated insulating barrier to be injected to semiconductor conduction band to a certain degree hindering excitation electron, namely reduces and injects electronics.Use TiCl 4as precursor solution to the method for light anode process gradually adopt by everybody, this method improves the efficiency of DSSC effectively, makes the electricity conversion of DSSC reach 7.36%.
Summary of the invention
In order to solve prior art problem, the object of the invention is to the deficiency overcoming prior art existence, a kind of method of modifying of dye-sensitized solar cell anode is provided, the mode utilizing metal ion mixing barrier layer to modify light anode forms the light anode modification layer of doping, improve DSSC photoelectric properties, the method is by doping and modification light anodic interface, the conduction band positions of semiconductor can be improved after doping thus suppress compound, thus effectively improving the photoelectric conversion efficiency of DSSC.
Create object for reaching foregoing invention, the present invention adopts following technical proposals:
A method of modifying for dye-sensitized solar cell anode, adopt metal ion mixing barrier layer process nano titania porous membrane, it comprises the steps:
A. the preparation of light anode modification solution: TiCl M ionizable metal salt compound being joined the 40mM prepared with certain proportion 4in solution, under the condition of room temperature, become the light anode modification solution of M: Ti=0.25-2% according to the molar ratio of ion; Preferably be mixed with the light anode modification solution of mol ratio M: Ti=0.75%; M ionizable metal salt preferably adopts Al 3+, Mg 2+, Zn 2+, Fe 3+, Fe 2+and Li +in any one ion or any several ion; M ionizable metal salt compound preferably adopts nitrate or chloride salt;
B. the modification of light anode: the titanium dioxide porous film after 500 DEG C of calcination processing is statically placed in the light anode modification solution prepared in described step a, and in 70 DEG C of insulation 30min, after deionized water rinsing, again through 500 DEG C of calcining 30min, obtain the titanium dioxide porous membrane after modifying, then the titanium dioxide porous membrane after modification is soaked in N719 dyestuff, leave standstill 24 hours, then take out, after ethanol purge, cold wind dries up, and namely obtains the light anode being coated with titanium dioxide porous film modified through M metal ion mixing barrier layer.
The method that the mode that the present invention utilizes metal ion mixing barrier layer to modify light anode improves DSSC photoelectric properties modify after light anode and the platinum of the same area of immersion dyestuff to together with electrode assembling, middle perfusion electrolyte, namely obtains DSSC.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
1. the present invention modifies light anode by metal ion mixing barrier layer, restrained effectively the compound of electronics, thus improves open circuit voltage and the short circuit current of battery, improves the photoelectric conversion efficiency of DSSC;
2. present invention process is simple, and reaction condition is gentle, does not need expensive equipment and raw material, is conducive to commercial introduction application.
Accompanying drawing explanation
Fig. 1 is the schematic diagram that the J-V curve of the DSSC prepared by comparative example and the embodiment of the present invention is compared.
Embodiment
Details are as follows for the preferred embodiments of the present invention:
embodiment 1
A method of modifying for dye-sensitized solar cell anode, adopt metal ion mixing barrier layer process nano titania porous membrane, improve DSSC photoelectric properties, its step is as follows:
A. the preparation of light anode modification solution:
By AlCl 3the TiCl of the 40mM prepared is joined with certain proportion 4in solution, under the condition of room temperature, stir 30min, be configured to the solution of Al: Ti=0.25% according to ion mol ratio;
B. the modification of light anode:
Titanium dioxide porous film after 500 DEG C of calcination processing is statically placed in the light anode modification solution of step a preparation, in 70 DEG C of insulation 30min, after deionized water rinsing, 500 DEG C of calcining 30min.Titanium dioxide porous membrane after modifying is soaked in N719 dyestuff, leaves standstill 24 hours, then take out, after ethanol purge, dry up with cold wind, namely obtain the light anode being coated with titanium dioxide porous film modified through metal ion mixing barrier layer.
The method that the mode that embodiment utilizes metal ion mixing barrier layer to modify light anode improves DSSC photoelectric properties modify after light anode and the platinum of the same area of immersion dyestuff to together with electrode assembling, middle perfusion electrolyte, can obtain DSSC.
It is the J-V curve of the DSSC adopting the method for modifying of the present embodiment dye-sensitized solar cell anode to prepare see curve 4 in table 1 and Fig. 1, figure.
embodiment 2
The present embodiment is substantially the same manner as Example 1, and special feature is:
A method of modifying for dye-sensitized solar cell anode, adopt metal ion mixing barrier layer process nano titania porous membrane, improve DSSC photoelectric properties, its step is as follows:
A. the preparation of light anode modification solution:
By AlCl 3the TiCl of the 40mM prepared is joined with certain proportion 4in solution, under the condition of room temperature, stir 30min, be configured to the solution of Al: Ti=0.5% according to ion mol ratio;
B. the modification of light anode:
Titanium dioxide porous film after 500 DEG C of calcination processing is statically placed in the light anode modification solution of step a preparation, in 70 DEG C of insulation 30min, after deionized water rinsing, 500 DEG C of calcining 30min.Titanium dioxide porous membrane after modifying is soaked in N719 dyestuff, leaves standstill 24 hours, then take out, after ethanol purge, dry up with cold wind, namely obtain the light anode being coated with titanium dioxide porous film modified through metal ion mixing barrier layer.
The method that the mode that the present embodiment utilizes metal ion mixing barrier layer to modify light anode improves DSSC photoelectric properties modify after light anode and the platinum of the same area of immersion dyestuff to together with electrode assembling, middle perfusion electrolyte, can obtain DSSC.
It is the J-V curve of the DSSC adopting the method for modifying of the present embodiment dye-sensitized solar cell anode to prepare see curve 5 in table 1 and Fig. 1, figure.
embodiment 3
The present embodiment and previous embodiment are substantially identical, and special feature is:
A method of modifying for dye-sensitized solar cell anode, adopt metal ion mixing barrier layer process nano titania porous membrane, improve DSSC photoelectric properties, its step is as follows:
A. the preparation of light anode modification solution:
By AlCl 3the TiCl of the 40mM prepared is joined with certain proportion 4in solution, under the condition of room temperature, stir 30min, be configured to the solution of Al: Ti=0.75% according to ion mol ratio;
B. the modification of light anode:
Titanium dioxide porous film after 500 DEG C of calcination processing is statically placed in the light anode modification solution of step a preparation, in 70 DEG C of insulation 30min, after deionized water rinsing, 500 DEG C of calcining 30min.Titanium dioxide porous membrane after modifying is soaked in N719 dyestuff, leaves standstill 24 hours, then take out, after ethanol purge, dry up with cold wind, namely obtain the light anode being coated with titanium dioxide porous film modified through metal ion mixing barrier layer.
The method that the mode that the present embodiment utilizes metal ion mixing barrier layer to modify light anode improves DSSC photoelectric properties modify after light anode and the platinum of the same area of immersion dyestuff to together with electrode assembling, middle perfusion electrolyte, can obtain DSSC.
It is the J-V curve of the DSSC adopting the method for modifying of the present embodiment dye-sensitized solar cell anode to prepare see curve 6 in table 1 and Fig. 1, figure.
embodiment 4
The present embodiment and previous embodiment are substantially identical, and special feature is:
A method of modifying for dye-sensitized solar cell anode, adopt metal ion mixing barrier layer process nano titania porous membrane, improve DSSC photoelectric properties, its step is as follows:
A. the preparation of light anode modification solution:
By AlCl 3the TiCl of the 40mM prepared is joined with certain proportion 4in solution, under the condition of room temperature, stir 30min, be configured to the solution of Al: Ti=2% according to ion mol ratio;
(2) modification of light anode:
Titanium dioxide porous film after 500 DEG C of calcination processing is statically placed in the light anode modification solution of step a preparation, in 70 DEG C of insulation 30min, after deionized water rinsing, 500 DEG C of calcining 30min.Titanium dioxide porous membrane after modifying is soaked in N719 dyestuff, leaves standstill 24 hours, then take out, after ethanol purge, dry up with cold wind, namely obtain the light anode being coated with titanium dioxide porous film modified through metal ion mixing barrier layer.
The method that the mode that the present embodiment utilizes metal ion mixing barrier layer to modify light anode improves DSSC photoelectric properties modify after light anode and the platinum of the same area of immersion dyestuff to together with electrode assembling, middle perfusion electrolyte, can obtain DSSC.
It is the J-V curve of the DSSC adopting the method for modifying of the present embodiment dye-sensitized solar cell anode to prepare see curve 7 in table 1 and Fig. 1, figure.
comparative example 1:
In order to contrast, this comparative example provides only TiCl 4process the preparation method as the DSSC of barrier layer, its step is as follows:
Titanium dioxide porous film after 500 DEG C of calcination processing is statically placed in the TiCl of 40mM 4solution, in 70 DEG C of insulation 30min, after deionized water rinsing, 500 DEG C of calcining 30min.This titanium dioxide porous membrane is soaked in N719 dyestuff, leaves standstill 24 hours, then take out, after ethanol purge, dry up with cold wind, namely obtain only TiCl 4process the light anode as barrier layer.
The light anode being coated with titanium dioxide porous film obtained through this comparative example and platinum of the same area are to together with electrode assembling, and middle perfusion electrolyte, can obtain DSSC.
See curve in table 1 and Fig. 1, figure 1 for adopting this comparative example TiCl 4as the J-V curve of DSSC prepared by the method for precursor solution to the process of light anode.
comparative example 2:
In order to contrast, the only AlCl that this comparative example example provides 3process the preparation method of the DSSC of barrier layer the most, step is substantially identical with comparative example 1, and special feature is, comprises the steps:
(1) preparation of barrier layer solution:
By AlCl 3be configured to the aqueous solution of 40mM under the condition of room temperature, stir 30min;
(2) preparation of light anode:
Titanium dioxide porous film after 500 DEG C of calcination processing is statically placed in the AlCl of the 40mM that step (1) is prepared 3barrier layer solution, in 70 DEG C of insulation 30min, after deionized water rinsing, 500 DEG C of calcining 30min.This titanium dioxide porous membrane is soaked in N719 dyestuff, leave standstill 24 hours, then take out, after ethanol purge, dry up with cold wind, namely obtain simple AlCl 3solution-treated is as the light anode being coated with titanium dioxide porous film of barrier layer.
Through the simple AlCl that this comparative example obtains 3solution-treated is as the light anode being coated with titanium dioxide porous film and the platinum of the same area of barrier layer to together with electrode assembling, and middle perfusion electrolyte, can obtain DSSC.
See curve in table 1 and Fig. 1, figure 2 for adopting this comparative example AlCl 3the J-V curve of DSSC prepared by the method for solution to the process of light anode.
comparative example 3:
In order to contrast, this comparative example provides the method utilizing the coated smooth anode of insulating barrier, and step is substantially identical with comparative example 2, and special feature is, it comprises the steps:
(1) preparation of the insulating barrier solution of coated smooth anode:
By AlCl 3be configured to the aqueous solution of 40mM under the condition of room temperature, stir 30min;
(2) modification of light anode:
Titanium dioxide porous film after 500 DEG C of calcination processing is statically placed in the TiCl of 40mM 4in solution, in 70 DEG C of insulation 30min, after deionized water rinsing, 500 DEG C of calcining 30min.This titanium dioxide porous membrane is statically placed in the 40mM AlCl that step (1) is prepared 3solution, in 70 DEG C of insulation 30min, after deionized water rinsing, 500 DEG C of calcining 30min.Titanium dioxide porous membrane after coated insulation layer is soaked in N719 dyestuff, leaves standstill 24 hours, then take out, after ethanol purge, dry up with cold wind, namely obtain the light anode of the coated titanium dioxide porous film of insulating barrier.
Light anode and the platinum of the same area of the immersion dyestuff after this comparative example utilizes the method for the coated smooth anode of insulating barrier to modify, to together with electrode assembling, middlely pour into electrolyte, can obtain DSSC.
It is the J-V curve of the DSSC adopting this comparative example to utilize the method for the coated smooth anode of insulating barrier to prepare see curve 3 in table 1 and Fig. 1, figure.
the test result of the DSSC that table 1. is prepared by comparative example and the embodiment of the present invention 1 ~ 4
Series Photoelectric conversion efficiency/% Open circuit voltage/V Short-circuit current density/mAcm -2 Fill factor, curve factor
Comparative example 1 7.36 0.75 17.69 0.55
Comparative example 2 5.44 0.82 12.11 0.55
Comparative example 3 7.97 0.80 16.34 0.62
Embodiment 1 8.08 0.77 17.93 0.58
Embodiment 2 8.03 0.76 18.39 0.57
Embodiment 3 8.64 0.76 18.32 0.62
Embodiment 4 8.10 0.75 17.56 0.61
In table 1 above, the test result of the barrier layer of different metal ion doping concentration being modified respectively the DSSC that the light anode that is coated with titanium dioxide porous film is prepared contrasts, the test result of a series of DSSC as can be seen from table 1 contrasts obviously: adopt the above embodiment of the present invention all effectively can improve the performance of DSSC, the equal photoelectric conversion efficiency that can make is greater than 8%, especially the effect of embodiment 3 is the most remarkable, the electricity conversion of the DSSC adopting the method for modifying of embodiment 3 dye-sensitized solar cell anode to prepare reaches 8.64%, TiCl is utilized than comparative example 1 4the electricity conversion of the DSSC prepared as the method for precursor solution to the process of light anode improves 17.39%, very has industrialization value.
embodiment 5:
The present embodiment and previous embodiment are substantially identical, and special feature is:
A method of modifying for dye-sensitized solar cell anode, adopt metal ion mixing barrier layer process nano titania porous membrane, improve DSSC photoelectric properties, its step is as follows:
A. the preparation of light anode modification solution:
By MgCl 2the TiCl of the 40mM prepared is joined with certain proportion 4in solution, under the condition of room temperature, stir 30min, be configured to the solution of Mg: Ti=0.75% according to ion mol ratio;
B. the modification of light anode:
Titanium dioxide porous film after 500 DEG C of calcination processing is statically placed in the light anode modification solution of step a preparation, in 70 DEG C of insulation 30min, after deionized water rinsing, 500 DEG C of calcining 30min.Titanium dioxide porous membrane after modifying is soaked in N719 dyestuff, leaves standstill 24 hours, then take out, after ethanol purge, dry up with cold wind, namely obtain the light anode being coated with titanium dioxide porous film modified through metal ion mixing barrier layer.
The method that the mode that the present embodiment utilizes metal ion mixing barrier layer to modify light anode improves DSSC photoelectric properties modify after light anode and the platinum of the same area of immersion dyestuff to together with electrode assembling, middle perfusion electrolyte, can obtain DSSC.
embodiment 6:
The present embodiment and previous embodiment are substantially identical, and special feature is:
A method of modifying for dye-sensitized solar cell anode, adopt metal ion mixing barrier layer process nano titania porous membrane, improve DSSC photoelectric properties, its step is as follows:
A. the preparation of light anode modification solution:
By ZnCl 2the TiCl of the 40mM prepared is joined with certain proportion 4in solution, under the condition of room temperature, stir 30min, be configured to the solution of Zn: Ti=0.75% according to ion mol ratio;
B. the modification of light anode:
Titanium dioxide porous film after 500 DEG C of calcination processing is statically placed in the light anode modification solution of step a preparation, in 70 DEG C of insulation 30min, after deionized water rinsing, 500 DEG C of calcining 30min.Titanium dioxide porous membrane after modifying is soaked in N719 dyestuff, leaves standstill 24 hours, then take out, after ethanol purge, dry up with cold wind, namely obtain the light anode being coated with titanium dioxide porous film modified through metal ion mixing barrier layer.
The method that the mode that the present embodiment utilizes metal ion mixing barrier layer to modify light anode improves DSSC photoelectric properties modify after light anode and the platinum of the same area of immersion dyestuff to together with electrode assembling, middle perfusion electrolyte, can obtain DSSC.
The present invention adopts different doped metallic elements to be different technical schemes, as long as adopt the solution of the mol ratio M:Ti=0.25%-2% of doped metallic elements and Ti element, all can reach above-mentioned effect, comprise the performance of the DSSC prepared by technique adopting above-described embodiment 5 and embodiment 6, the equal photoelectric conversion efficiency that can make is greater than 8%, thus realize modifying light sun by metal ion mixing barrier layer, pole restrained effectively the compound of electronics, thus the open circuit voltage of raising battery and short circuit current are to improve the photoelectric conversion efficiency of DSSC.
By reference to the accompanying drawings the embodiment of the present invention is illustrated above; but the invention is not restricted to above-described embodiment; multiple change can also be made according to the object of innovation and creation of the present invention; change, the modification made under all Spirit Essences according to technical solution of the present invention and principle, substitute, combination, to simplify; all should be the substitute mode of equivalence; as long as goal of the invention according to the invention; only otherwise deviate from know-why and the inventive concept of the method for modifying of dye-sensitized solar cell anode of the present invention, all protection scope of the present invention is belonged to.

Claims (3)

1. a method of modifying for dye-sensitized solar cell anode, is characterized in that, adopt metal ion mixing barrier layer process nano titania porous membrane, it comprises the steps:
A. the preparation of light anode modification solution: TiCl M ionizable metal salt compound being joined the 40mM prepared with certain proportion 4in solution, under the condition of room temperature, become the light anode modification solution of M: Ti=0.25-2% according to the molar ratio of ion;
B. the modification of light anode: the titanium dioxide porous film after 500 DEG C of calcination processing is statically placed in the light anode modification solution prepared in described step a, and in 70 DEG C of insulation 30min, after deionized water rinsing, again through 500 DEG C of calcining 30min, obtain the titanium dioxide porous membrane after modifying, then the titanium dioxide porous membrane after modification is soaked in N719 dyestuff, leave standstill 24 hours, then take out, after ethanol purge, cold wind dries up, and namely obtains the light anode being coated with titanium dioxide porous film modified through M metal ion mixing barrier layer.
2. the method for modifying of dye-sensitized solar cell anode according to claim 1 and 2, is characterized in that: in described step a, and M ionizable metal salt adopts Al 3+, Mg 2+, Zn 2+, Fe 3+, Fe 2+and Li +in any one ion or any several ion, then through described step b, form corresponding metal ion mixing.
3. the method for modifying of dye-sensitized solar cell anode according to claim 1 and 2, is characterized in that: in described step a, and M ionizable metal salt compound is nitrate or chloride salt.
CN201410474338.0A 2014-09-17 2014-09-17 Modification method of photo-anode of dye-sensitized solar cell Pending CN104240957A (en)

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