CN101630596A - Composite membrane counter electrode used for dye-sensitized solar cells and preparation method thereof - Google Patents
Composite membrane counter electrode used for dye-sensitized solar cells and preparation method thereof Download PDFInfo
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- CN101630596A CN101630596A CN200910072716A CN200910072716A CN101630596A CN 101630596 A CN101630596 A CN 101630596A CN 200910072716 A CN200910072716 A CN 200910072716A CN 200910072716 A CN200910072716 A CN 200910072716A CN 101630596 A CN101630596 A CN 101630596A
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Abstract
The invention relates to a composite membrane counter electrode used for dye-sensitized solar cells (DSSC) and a preparation method thereof, solving the problem that platinum counter electrodes of the existing DSSC have high preparation cost. The composite membrane counter electrode of the invention is formed by connecting a conductive substrate, a carbon material membrane and a polythiophene membrane. The preparation method of the invention comprises the following steps: first preparing electrophoretic liquid of the carbon material and then electrophoretically depositing the carbon material membrane on the conductive substrate; preparing electrodeposition liquid of thiophene and depositing the polythiophene membrane on the carbon material membrane by cyclic voltammetry to obtain the carbon material/polythiophene composite membrane counter electrode. The composite membrane counter electrode of the invention has good catalytic performance, good electrochemical stability and low preparation cost. The photoelectric conversion efficiency of the DSSC based on the composite membrane counter electrode of the invention reaches 4.721%, which is equivalent to that of the existing DSSC based on the Pt counter electrodes.
Description
Technical field
The composite membrane that the present invention relates to a kind of DSSC particularly relates to material with carbon element/polythiophene class composite membrane to electrode and preparation method thereof to electrode and preparation method thereof.
Background technology
Current regenerative resource constantly consumes, and the energy pressure that the mankind face continues aggravation, and the research and development solar cell has apparent, very important strategic importance.DSSC is a kind of novel Optical Electro-Chemistry solar cell, main by dye sensitized nano crystal electrode, electrolyte and be loaded with catalyst electrode part is grouped into, has lower cost, easy preparation technology and good Environmental compatibility have good application prospects.
To the important component part of electrode as DSSC, be mainly used in the collection electronics, also having a main effect is catalytic action, quickens I
-/ I
3 -And the electron exchange speed between the cathode electronics, therefore need be to electrode is modified, to improve its catalytic performance.The main at present method of modifying that adopts is that platinum is modified, and has the electro-conductive glass of platinum catalyst to constitute by load usually.Platinum can make the charge migration on the electrode and electrolyte liquor interface is rapidly and efficiently carried out, and suppresses dark current, improves the open circuit voltage of battery.But the costliness of platinum and rare causes the kind electrode preparation cost higher.
Summary of the invention
The objective of the invention is to the invention provides a kind of composite membrane of DSSC that is used for to electrode and preparation method thereof in order to solve the platinum problem high of existing DSSC to the electrode preparation cost.
The composite membrane that the present invention is a kind of to be used for DSSC to electrode from the bottom to top successively by conductive substrates, material with carbon element film and polythiophene class film are formed by connecting by the acting in conjunction of active force between intermolecular force and atom, and described polythiophene class film is polythiophene film or polythiofuran derivative film.
The present invention is used for the preparation method of the composite membrane of DSSC to electrode, realizes by following steps:
One, electrophoretic deposition prepares the material with carbon element film
The configuration of a, material with carbon element electrophoresis liquid: material with carbon element is added in the mixed acid, soak 5～7h at 50 ℃～70 ℃ following constant temperature then, filter then, with distilled water the material with carbon element that filters out is washed to cleaning solution again and be neutral, then material with carbon element is got the material with carbon element of finishing at 50 ℃～70 ℃ following vacuumize 10～15h, and then the material with carbon element of finishing is distributed in the aprotic organic solvent, sonic oscillation disperses to leave standstill the material with carbon element electrophoresis liquid that 20～40min obtains stable suspension behind 20～40min again; Wherein, described mixed acid is the mixture of 3: 1 by volume ratios of red fuming nitric acid (RFNA) of the concentrated sulfuric acid and 69% (quality) of 98% (quality), the ratio of material with carbon element quality and mixed acid volume is 1g: 60～100mL, and the material with carbon element quality of finishing and the ratio of aprotic organic solvent volume are 1mg: 1mL;
The preparation of b, material with carbon element film: in the material with carbon element electrophoresis liquid, with conductive substrates as anode, platinum electrode is as negative electrode, negative electrode and anode spacing are from 0.5～1.0cm, under direct current 40～60V voltage, electrophoresis 10～20 seconds, deposit carbon material film in substrate, the conductive substrates that will deposit the material with carbon element film then obtains the material with carbon element film at 70 ℃～90 ℃ following vacuumize 3～5h on conductive substrates;
Two, composite membrane is to the preparation of electrode
The configuration of a, thiophene or thiophene derivant electrodeposit liquid: thiophene or thiophene derivant monomer be dissolved in obtain thiophene or thiophene derivant electrodeposit liquid in the BFEE, the concentration of thiophene or thiophene derivant is 15～20mmol/L;
B, composite membrane is to the preparation of electrode: in thiophene or thiophene derivant electrodeposit liquid, with the sweep speed is 0.05V/s, with electrochemical workstation with three-electrode system, with the conductive substrates that deposits the material with carbon element film as work electrode, the platinum electrode conduct is to electrode, saturated calomel electrode or silver/silver chloride electrode are as reference electrode, initial potential is set is-0.8V, in the sweep limits of-0.8V～1.6V, carry out cyclic voltammetry scan 10～20 circles, take out work electrode then, use deionized water rinsing, obtain material with carbon element/polythiophene class composite membrane to electrode at 70 ℃～90 ℃ following vacuumize 10～15h again, the composite membrane that promptly is used for DSSC is to electrode; Described polythiophene class is polythiophene or polythiofuran derivative.
The composite membrane that is used for DSSC of the present invention is to the continuous even compact of electrode, and adhesion is strong between the adjacent layer, long service life, and cost is low.The continuous even compact of material with carbon element film, has very big specific area, good electron conductivity, stable chemical property, very high catalytic activity, simultaneously, have polythiophene class film that the novel thiophene compounds of conjugated structure and good charge transport properties obtains and be fine and close solid particle film continuously, has the conductance height, the advantage that electrochemical reversibility is strong, and the polythiophene class compound can form firm good the contact with substrate at a lower temperature, be convenient to the preparation of large scale electrode, under the interaction of material with carbon element film and polythiophene class film, make composite membrane of the present invention good to the electrode catalyst performance, the electrochemical stability performance is good, and size is controlled.Based on composite membrane of the present invention the photoelectric conversion efficiency of the DSSC of electrode is reached 4.721%, can reach with based on the existing conventional P t level suitable to the DSSC of electrode.
Preparation method's manufacturing cycle of the present invention is short, preparation technology is simple, and film forming is fast, and film thickness is controlled.Preparation process does not need the harsh conditions of HTHP, and energy consumption is little, and cost of material is low, and cost is low.What prepare is membrane electrode to electrode, and film has very big advantage aspect reducing cost: the one, after the realization filming, can greatly save material; The 2nd, film adopts the low temperature process technology, not only helps saving energy and reduce the cost, and is convenient to adopt inexpensive substrate; The 3rd, high by battery conversion efficiency height, the stability of membrane electrode assembling, have a large-scale production ability.Therefore the present invention has good suitability for industrialized production potentiality.
Preparation method of the present invention need not add active additive in material with carbon element film preparation process, effectively guaranteed the electrical property and the catalytic performance of material with carbon element.The composite membrane that is used for DSSC that the present invention obtains is good to the electrode catalyst performance, and electrochemical stability is good, conductance height, photoelectric conversion efficiency height.
Description of drawings
Fig. 1 is the structural representation that is used for the composite membrane of DSSC to electrode of the present invention; Fig. 2 is the SEM pattern phenogram of the multi-wall carbon nano-tube film that step 1 obtains in the embodiment 15; Fig. 3 is the AFM pattern phenogram of the multi-wall carbon nano-tube film that step 1 obtains in the embodiment 15; Fig. 4 is the AFM pattern phenogram of the composite membrane that is used for DSSC that obtains of embodiment 15 to electrode (multi-walled carbon nano-tubes/polythiophene composite film is to electrode); Fig. 5 is based on the voltage-to-current curve chart of the multi-walled carbon nano-tubes/polythiophene composite film of embodiment 15 to the DSSC of electrode.Fig. 6 is the cyclic voltammetry scan curve chart of the multi-walled carbon nano-tubes/polythiophene composite film that is used for DSSC that obtains of embodiment 15 to electrode.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: the composite membrane that present embodiment is used for DSSC is formed by connecting by the acting in conjunction by active force between intermolecular force and atom of conductive substrates (1), material with carbon element film (2) and polythiophene class film (3) from the bottom to top successively to electrode, and described polythiophene class film is polythiophene film or polythiofuran derivative film.
The composite membrane that is used for DSSC of present embodiment to the structural representation of electrode as shown in Figure 1.The composite membrane that is used for DSSC is evenly fine and close to electrode structure, and adhesion is strong between the adjacent layer, long service life, and good stability, catalytic performance is good, the conductance height, size is controlled.Based on the composite membrane that is used for DSSC of present embodiment the photoelectric conversion efficiency of the DSSC of electrode is reached 4.721%, can reach with based on the existing conventional P t level suitable to the DSSC of electrode.Wherein, DSSC encapsulates combination according to existing sandwich laminated type compound mode in the present embodiment, and anode (work electrode) is TiO
2Electrode, electrolyte are by lithium iodide (LiI), iodine (I
2), tert .-butylpyridine and 1-butyl-3-methylimidazole iodine (BMIm) is dissolved in disposing in acetonitrile and the valeronitrile mixed solvent and forms, wherein, LiI and I
2Mol ratio be 1: 0.5, the mol ratio of LiI and tert .-butylpyridine is 1: 6, the mol ratio of LiI and BMIm is 1: 6, the ratio of LiI quality and mixed solvent volume is 1g: 50mL, acetonitrile is 85: 15 with the mixed volume ratio of valeronitrile in the mixed solvent.
Embodiment two: present embodiment and embodiment one are different is that the thickness of material with carbon element film (2) is 1～10 μ m, and the thickness of polythiophene class film (3) is 1～5 μ m.Other parameter is identical with embodiment one.
Embodiment three: present embodiment is different with embodiment one or two is that conductive substrates (1) is selected from electro-conductive glass, stainless steel metal sheet or is coated with the insulating material of conductive metal film.Other parameter is identical with embodiment one or two.
Conducting metal described in the present embodiment is copper, nickel, zinc, titanium or tin.
Embodiment four: what present embodiment and embodiment one, two or three were different is that material with carbon element is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, graphite powder or carbonaceous mesophase spherules.Other parameter is identical with embodiment one, two or three.
Embodiment five: what present embodiment and embodiment one to four were different is that polythiofuran derivative is poly-(3-C
1-12Alkylthrophene), poly-(3-phenyl thiophene), poly-(3-ethanol based thiophene), poly-(3,4-ethylene group dioxy thiophene or poly-(3, the 4-dimethoxy-thiophene).Other parameters are identical with embodiment one to four.
Embodiment six: present embodiment such as embodiment one described a kind of preparation method who is used for the composite membrane of DSSC to electrode, realize by following steps:
One, electrophoretic deposition prepares the material with carbon element film
The configuration of a, material with carbon element electrophoresis liquid: material with carbon element is added in the mixed acid, soak 5～7h at 50 ℃～70 ℃ following constant temperature then, and then filter, with distilled water the material with carbon element that filters out is washed to cleaning solution again and be neutral, then material with carbon element is got the material with carbon element of finishing at 50 ℃～70 ℃ following vacuumize 10～15h, and then the material with carbon element of finishing is distributed in the aprotic organic solvent, sonic oscillation disperses to leave standstill the material with carbon element electrophoresis liquid that 20～40min obtains stable suspension behind 20～40min again; Wherein, described mixed acid is the mixture of 3: 1 by volume ratios of red fuming nitric acid (RFNA) of the concentrated sulfuric acid and 69% (quality) of 98% (quality), the ratio of material with carbon element quality and mixed acid volume is 1g: 60～100mL, and the material with carbon element quality of finishing and the ratio of aprotic organic solvent volume are 1mg: 1mL;
The preparation of b, material with carbon element film: in the material with carbon element electrophoresis liquid, with conductive substrates as anode, platinum electrode is as negative electrode, negative electrode and anode spacing are from 0.5～1.0cm, under direct current 40～60V voltage, electrophoresis 10～20 seconds, deposit carbon material film in substrate, the conductive substrates that will deposit the material with carbon element film then obtains the material with carbon element film at 70 ℃～90 ℃ following vacuumize 3～5h on conductive substrates;
Two, composite membrane is to the preparation of electrode
The configuration of a, thiophene or thiophene derivant electrodeposit liquid: thiophene or thiophene derivant monomer be dissolved in obtain thiophene or thiophene derivant electrodeposit liquid in the BFEE, the concentration of thiophene or thiophene derivants is 15～20mmol/L;
B, composite membrane is to the preparation of electrode: in thiophene or thiophene derivant electrodeposit liquid, with the sweep speed is 0.05V/s, with electrochemical workstation with three-electrode system, with the conductive substrates that deposits the material with carbon element film as work electrode, the platinum electrode conduct is to electrode, saturated calomel electrode or silver/silver chloride electrode are as reference electrode, initial potential is set is-0.8V, in the sweep limits of-0.8V～1.6V, carry out cyclic voltammetry scan 10～20 circles, take out work electrode then, use deionized water rinsing, obtain material with carbon element/polythiophene class composite membrane to electrode at 70 ℃～90 ℃ following vacuumize 10～15h again, the composite membrane that promptly is used for DSSC is to electrode, and described polythiophene class is polythiophene or polythiofuran derivative.
Preparation method's manufacturing cycle of present embodiment is short, preparation technology is simple, and film forming is fast, and film thickness is controlled.Preparation process does not need the harsh conditions of HTHP, and energy consumption is little, and cost of material is low, and cost reduces.
Embodiment seven: present embodiment and embodiment six are different is that material with carbon element is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, graphite powder or carbonaceous mesophase spherules in a step of step 1.Other parameter is identical with embodiment six.
The carbon nano-tube of present embodiment is provided by nanometer port, Shenzhen or Chengdu organic chemistry, and graphite powder is that Yong Tong carbon element factory, Handan, Hebei produces.
The preparation method of carbonaceous mesophase spherules is in the present embodiment: under 100 ℃, in coal tar or pitch, add pyridine, filter then and remove insoluble matter, coal tar or pitch after will purifying then join in the autoclave, be warmed up to 260 ℃, stir after 1 hour, carry out polymerization reaction 5h after being raised to 400 ℃ with the intensification degree of 4 ℃/min again, product filtration under 250 ℃ with polymerization reaction obtains filter residue then, use pyridine extracting filter residue to colourless again, then filter residue vacuumize is obtained carbonaceous mesophase spherules, and, obtain the graphitization carbonaceous mesophase spherules through 2900 ℃ of heat treatments.
Embodiment eight: present embodiment is different with embodiment six or seven is that aprotic organic solvent is acetonitrile, acetone, carbonic ester, glyoxaline ion liquid or ethers in a step of step 1.Other step and parameter are identical with embodiment six or seven.
Glyoxaline ion liquid is that anion is that (chemical formula is [EMIm] CF for the alkyl substituted imidazole iodine of trifluoromethanesulfonic acid root, tetrafluoroborate or hexafluoro-phosphate radical in the present embodiment
38O
3, [EMIm] BF
4Perhaps [EMIm] PF
6, wherein [EMIm] is 1-ethyl-3-methylimidazole cation).Ethers is dimethoxymethane or 1,2-dimethoxy ethane.
Embodiment nine: present embodiment and embodiment six, seven or eight are different is that conductive substrates is selected from electro-conductive glass, stainless steel metal sheet or is coated with the insulating material of conductive metal film in the b step of step 1.Other step and parameter are identical with embodiment six, seven or eight.
Conducting metal described in the present embodiment is copper, nickel, zinc, titanium or tin.
Embodiment ten: present embodiment and embodiment six to nine are different is that electrophoresis time is 10 seconds in the b step of step 1.Other step and parameter are identical with embodiment six to nine.
Embodiment 11: present embodiment and embodiment six to ten are different is that thiophene derivant is 3-C in a step of step 2
1-12Alkylthrophene, 3-phenyl thiophene, 3-ethanol based thiophene, 3,4-ethylene group dioxy thiophene or 3,4-dimethoxy-thiophene.Other step and parameter are identical with embodiment six to ten.
Embodiment 12: present embodiment and embodiment six to 11 are different is that polythiophene class is polythiophene or polythiofuran derivative in the b step of step 2, and wherein polythiofuran derivative is poly-(3-C
1-12Alkylthrophene), poly-(3-phenyl thiophene), poly-(3-ethanol based thiophene), poly-(3,4-ethylene group dioxy thiophene or poly-(3, the 4-dimethoxy-thiophene).Other step and parameter are identical with embodiment six to 11.
Table 1 is at 90mW/cm
2The simulated solar luminous intensity under, the composite membrane that obtains being used for DSSC based on present embodiment is carried out the test of photoelectric current-photovoltage volt-ampere characteristic to the DSSC of electrode.
Present embodiment is assembled electrode according to the composite membrane that the compound mode of embodiment one described DSSC will be used for DSSC, then at 90mW/cm
2The simulated solar luminous intensity under, the composite membrane that obtains based on present embodiment is carried out the test of photoelectric current-photovoltage volt-ampere characteristic to the DSSC of electrode, test result is as shown in table 1.
Table 1
| Composite membrane is to electrode | Electrophoresis time (s) | The cyclic voltammetry scan number of times | Photoelectric conversion efficiency |
| Single Walled Carbon Nanotube/polythiophene | ??15 | 10 circles | ??4.606％ |
| Single Walled Carbon Nanotube/poly-3 methyl thiophene | ??10 | 10 circles | ??4.108％ |
| Multi-walled carbon nano-tubes/polythiophene | ??15 | 15 circles | ??4.721％ |
| Multi-walled carbon nano-tubes/poly-3-ethylthiophene | ??10 | 15 circles | ??4.052％ |
| Multi-walled carbon nano-tubes/poly-3-ethanol based thiophene | ??10 | 15 circles | ??4.089％ |
| Middle phase microballoon carbon/ |
??10 | 15 circles | ??3.665％ |
| Middle phase microballoon carbon/polythiophene | ??15 | 15 circles | ??3.841％ |
| Graphite/poly-3-ethylthiophene | ??15 | 10 circles | ??3.568％ |
| Graphite/poly-(3, the 4-dimethoxy-thiophene) | ??15 | 10 circles | ??3.901％ |
As shown in Table 1, the composite membrane that is used for DSSC that obtains based on present embodiment is to the electricity conversion height of the DSSC of electrode, reach 4.721%, it can reach the photoelectric conversion efficiency to the dye sensitization of solar of electrode based on Pt.
Embodiment 13: present embodiment and embodiment six to 12 are different is that thiophene monomer and thiophene derivant monomer are that effluent south Puyang Huicheng Chemicals Co., Ltd or Japanese TCI change into industrial (Shanghai) Co., Ltd. and produce in a step of step 2.Other step and parameter are identical with embodiment six to 12.
Embodiment 14: present embodiment and embodiment six to 13 are different is to carry out cyclic voltammetry scan 15 circles in the b step of step 2.Other step and parameter are identical with embodiment six to 13.
Embodiment 15: present embodiment and embodiment six are different, and to be the composite membrane that is used for DSSC realize by following steps the preparation method of electrode:
One, electrophoretic deposition prepares multi-wall carbon nano-tube film
1, the 1g multi-walled carbon nano-tubes is added in the 80mL mixed acid, soak 6h at 60 ℃ of following constant temperature then, and then filter, with distilled water the material with carbon element that filters out is washed to cleaning solution again and be neutral, then material with carbon element is got the material with carbon element of finishing at 60 ℃ of following vacuumize 12h, and then the material with carbon element of finishing is distributed in the 1L acetonitrile solvent, sonic oscillation disperses to leave standstill the material with carbon element electrophoresis liquid that 30min obtains stable suspension behind the 30min again;
2, in the material with carbon element electrophoresis liquid, with electro-conductive glass as anode, platinum electrode is as negative electrode, negative electrode and anode spacing are from 1.0cm, under direct current 50V voltage, electrophoresis 15 seconds, deposit carbon material film on electro-conductive glass, the electro-conductive glass that will deposit the material with carbon element film then obtains multi-wall carbon nano-tube film at 80 ℃ of following vacuumize 4h on electro-conductive glass;
Two, composite membrane is to the preparation of electrode
1,0.06～0.07g thiophene monomer is dissolved in obtains thiophene electroprecipitation liquid in the 25mL BFEE;
2, in the above-mentioned thiophene electrodeposit liquid that obtains, carry out cyclic voltammetry scan 15 circles, take out work electrode then, use deionized water rinsing, obtain multi-walled carbon nano-tubes/polythiophene composite film to electrode at 80 ℃ of following vacuumize 12h again, the composite membrane that promptly is used for DSSC is to electrode.Other step and parameter are identical with embodiment six.
The multi-wall carbon nano-tube film that step 1 obtains in the present embodiment carries out scanning electron microscopy (SEM) respectively and atomic force microscope (AFM) characterizes, and the result respectively as shown in Figures 2 and 3.As seen from Figure 2, the continuous even compact of multi-wall carbon nano-tube film, as shown in Figure 3, the specific area of multi-wall carbon nano-tube film is big.Present embodiment is carried out atomic force microscope (AFM) to the composite membrane that is used for DSSC that obtains to electrode (multi-walled carbon nano-tubes/polythiophene composite film is to electrode) and is characterized, and the result as shown in Figure 4.Can be seen that by Fig. 4 polythiophene film is the particle membrane of continuous even compact, specific area is big.
The composite membrane that is used for DSSC of present embodiment is good to the electrode catalyst performance, according to embodiment one described DSSC compound mode the composite membrane that is used for DSSC of present embodiment is assembled electrode (multi-walled carbon nano-tubes/polythiophene composite film is to electrode), then will be based on the multi-walled carbon nano-tubes/polythiophene composite film of present embodiment to the DSSC of electrode at 90mW/cm
2The simulated solar luminous intensity under carry out the test of photoelectric current-photovoltage volt-ampere characteristic, test result is shown in a curve among Fig. 5, the photoelectric conversion efficiency height is 4.721%, fill factor, curve factor is 0.582, short-circuit current density is 10.507mA/cm
2, open circuit voltage is 695mV.As a comparison, we utilize pyrolysismethod to prepare Pt to electrode, and after according to embodiment one described DSSC compound mode Pt being assembled electrode, utilize said method to test, test result is shown in b curve among Fig. 5, existing is 5.667% based on Pt to the photoelectric conversion efficiency of the DSSC of electrode, and fill factor, curve factor is 0.632, and short-circuit current density is 10.842mA/cm
2, open circuit voltage is 746mV.Contrast as can be known by a, b curve among Fig. 5, the composite membrane that is used for DSSC of present embodiment is to the excellent catalytic effect of electrode (multi-walled carbon nano-tubes/polythiophene composite film is to electrode), based on its photoelectric conversion efficiency of DSSC can reach with existing based on Pt to the DSSC of electrode quite.
Present embodiment is in BFEE, with the sweep speed is 0.05V/s, with electrochemical workstation with three-electrode system, with the composite membrane that is used for DSSC of present embodiment to electrode (multi-walled carbon nano-tubes/polythiophene composite film is to electrode) as work electrode, the platinum electrode conduct is to electrode, silver/silver chloride electrode is as reference electrode, initial potential is set is-0.8V, in the sweep limits of-0.8V～1.6V, carry out cyclic voltammetry scan 10 circles, the cyclic voltammetry curve figure that obtains, as shown in Figure 6.As shown in Figure 6, the multi-walled carbon nano-tubes/polythiophene composite film of present embodiment is good to the electrochemical reversibility of electrode, stable electrochemical property.
Claims (10)
1, a kind of composite membrane of DSSC that is used for is to electrode, it is characterized in that the composite membrane that is used for DSSC is formed by connecting by the acting in conjunction by active force between intermolecular force and atom of conductive substrates (1), material with carbon element film (2) and polythiophene class film (3) from the bottom to top successively to electrode, described polythiophene class film is polythiophene film or polythiofuran derivative film.
2, a kind of composite membrane that is used for DSSC according to claim 1 is to electrode, and the thickness that it is characterized in that material with carbon element film (2) is 1～10 μ m, and the thickness of polythiophene class film (3) is 1～5 μ m.
3, a kind of composite membrane that is used for DSSC according to claim 1 and 2 is to electrode, it is characterized in that described conductive substrates (1) is selected from electro-conductive glass, stainless steel metal sheet or is coated with the insulating material of conductive metal film.
4, a kind of composite membrane that is used for DSSC according to claim 3 is characterized in that to electrode material with carbon element is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, graphite powder or carbonaceous mesophase spherules.
5, according to claim 1,2 or 4 described a kind of composite membranes that are used for DSSC to electrode, it is characterized in that polythiofuran derivative is poly-(3-C
1-12Alkylthrophene), poly-(3-phenyl thiophene), poly-(3-ethanol based thiophene), poly-(3,4-ethylene group dioxy thiophene) or poly-(3, the 4-dimethoxy-thiophene).
6, the preparation method who is used for the composite membrane of DSSC to electrode as claimed in claim 1, the composite membrane that it is characterized in that being used for DSSC is realized by following steps the preparation method of electrode:
One, electrophoretic deposition prepares the material with carbon element film
The configuration of a, material with carbon element electrophoresis liquid: material with carbon element is added in the mixed acid, soak 5～7h at 50 ℃～70 ℃ following constant temperature then, filter then, with distilled water the material with carbon element that filters out is washed to cleaning solution again and be neutral, then material with carbon element is got the material with carbon element of finishing at 50 ℃～70 ℃ following vacuumize 10～15h, and then the material with carbon element of finishing is distributed in the aprotic organic solvent, sonic oscillation disperses to leave standstill the material with carbon element electrophoresis liquid that 20～40min obtains stable suspension behind 20～40min again; Wherein, described mixed acid is the mixture of 3: 1 by volume ratios of red fuming nitric acid (RFNA) of the concentrated sulfuric acid and 69% (quality) of 98% (quality), the ratio of material with carbon element quality and mixed acid volume is 1g: 60～100mL, and the material with carbon element quality of finishing and the ratio of aprotic organic solvent volume are 1mg: 1mL;
The preparation of b, material with carbon element film: in the material with carbon element electrophoresis liquid, with conductive substrates as anode, platinum electrode is as negative electrode, negative electrode and anode spacing are from 0.5～1.0cm, under direct current 40～60V voltage, electrophoresis 10～20 seconds, deposit carbon material film in substrate, the conductive substrates that will deposit the material with carbon element film then obtains the material with carbon element film at 70 ℃～90 ℃ following vacuumize 3～5h on conductive substrates;
Two, composite membrane is to the preparation of electrode
The configuration of a, thiophene or thiophene derivant electrodeposit liquid: thiophene or thiophene derivant monomer be dissolved in obtain thiophene or thiophene derivant electrodeposit liquid in the BFEE, the concentration of thiophene or thiophene derivants is 15～20mmol/L;
B, composite membrane is to the preparation of electrode: in thiophene or thiophene derivant electrodeposit liquid, with the sweep speed is 0.05V/s, with electrochemical workstation with three-electrode system, with the conductive substrates that deposits the material with carbon element film as work electrode, the platinum electrode conduct is to electrode, saturated calomel electrode or silver/silver chloride electrode are as reference electrode, initial potential is set is-0.8V, in the sweep limits of-0.8V～1.6V, carry out cyclic voltammetry scan 10～20 circles, take out work electrode then, use deionized water rinsing, obtain material with carbon element/polythiophene class composite membrane to electrode at 70 ℃～90 ℃ following vacuumize 10～15h again, the composite membrane that promptly is used for DSSC is to electrode, and described polythiophene class is polythiophene or polythiofuran derivative.
7, the preparation method who is used for the composite membrane of DSSC to electrode according to claim 6 is characterized in that material with carbon element is Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, graphite or carbonaceous mesophase spherules in a step of step 1.
8,, it is characterized in that conductive substrates in the b step of step 1 is selected from electro-conductive glass, stainless steel metal sheet or is coated with the insulating material of conductive metal film according to claim 6 or the 7 described preparation methods that are used for the composite membrane of DSSC to electrode.
9, the preparation method who is used for the composite membrane of DSSC to electrode according to claim 8 is characterized in that in the step 1 in the b step electrophoresis 15 seconds.
10,, it is characterized in that thiophene derivant is 3-C in a step of step 2 according to claim 6, the 7 or 9 described preparation methods that are used for the composite membrane of DSSC to electrode
1-12Alkylthrophene, 3-phenyl thiophene, 3-ethanol based thiophene, 3,4-ethylene group dioxy thiophene or 3,4-dimethoxy-thiophene.
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| CN101923958A (en) * | 2010-09-08 | 2010-12-22 | 天津大学 | Method for preparing energy storage electrode of dye-sensitized solar battery |
| WO2012040893A1 (en) * | 2010-09-27 | 2012-04-05 | 海洋王照明科技股份有限公司 | Conducting polymer-carbon material combined counter electrode and manufacturing mathod thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101923958A (en) * | 2010-09-08 | 2010-12-22 | 天津大学 | Method for preparing energy storage electrode of dye-sensitized solar battery |
| WO2012040893A1 (en) * | 2010-09-27 | 2012-04-05 | 海洋王照明科技股份有限公司 | Conducting polymer-carbon material combined counter electrode and manufacturing mathod thereof |
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