CN101630595B - Preparation method of composite membrane counter electrode used for dye-sensitized solar cells - Google Patents
Preparation method of composite membrane counter electrode used for dye-sensitized solar cells Download PDFInfo
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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 comprises a conductive substrate, a manganese dioxide membrane and a conductive polymer membrane. The preparation method of the invention comprises the following steps: first preparing electrophoretic liquid of the manganese dioxide and then electrophoretically depositing the manganese dioxide membrane on the conductive substrate; preparing electrodeposition liquid of a conductive polymer and depositing the conductive polymer membrane on the manganese dioxide membrane by cyclic voltammetry to obtain the composite membrane counter electrode used for DSSC. The composite membrane counter electrode of the invention has good catalytic performance and low preparation cost. The photoelectric conversion efficiency of the DSSC based on the composite membrane counter electrode of the invention reaches 3.85%, which is equivalent to that of the existing DSSC based on the Pt counter electrodes.
Description
Technical field
The present invention relates to the preparation method of a kind of composite membrane of DSSC, particularly relate to MnO electrode
2/ conductive polymer composite film is to the preparation method of electrode.
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 preparation method who is used for the composite membrane of DSSC to electrode 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, is formed by connecting under the acting in conjunction by active force between intermolecular force and atom of manganese dioxide membrane and conducting polymer thin film from the bottom to top successively by conductive substrates to electrode.
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 manganese dioxide membrane
The configuration of a, manganese dioxide electrophoresis liquid: manganese dioxide is dispersed in the aprotic organic solvent, and then adding TBAH, stir after 24 hours, left standstill 1 hour, centrifugal then, again manganese dioxide is scattered in the aprotic organic solvent after the drying, then sonic oscillation 20～40min, leave standstill 20～40min again, obtain the manganese dioxide electrophoresis liquid of stable suspension; The proportionate relationship that wherein said twice manganese dioxide is scattered in aprotic organic solvent is: the ratio of manganese dioxide quality and aprotic organic solvent volume is 6～7g: 350mL, and the ratio of manganese dioxide quality and TBAH volume is 6～7g: 150mL;
The preparation of b, manganese dioxide membrane: in the manganese dioxide 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 3～5 seconds deposits manganese dioxide membrane on conductive substrates, the conductive substrates that will deposit manganese dioxide membrane then obtains manganese dioxide membrane at 70 ℃～90 ℃ following vacuumize 20～24h on conductive substrates;
Two, composite membrane is to the preparation of electrode
The configuration of a, conducting polymer monomer electrodeposit liquid: the conducting polymer monomer is dissolved in obtains conducting polymer monomer electrodeposit liquid in the BFEE, the concentration of conducting polymer monomer is 15～20mmol/L;
B, composite membrane is to the preparation of electrode: in conducting polymer monomer electrodeposit liquid, with the sweep speed is 0.05V/s, with electrochemical workstation with three-electrode system, with the conductive substrates that deposits manganese dioxide membrane 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 manganese dioxide/conductive polymer composite film to electrode at 70 ℃～90 ℃ following vacuumize 10～15h again, the composite membrane that promptly is used for DSSC is to electrode.
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 manganese dioxide membrane, have very big specific area, good electron conductivity, stable chemical property, very high catalytic activity, simultaneously, have conducting polymer thin film that the novel conductive polymer of conjugated structure and good charge transport properties obtains and be fine and close solid particle film continuously, have conductance height, advantage that electrochemical reversibility is strong, and conducting polymer can form firm good the contact with substrate at a lower temperature, is convenient to the preparation of large scale electrode.The interaction of manganese dioxide membrane and conducting polymer thin film, manganese dioxide membrane and conducting polymer thin film that feasible nano semiconductor manganese dioxide particle with high surface energy forms are combined with each other, thin polymer film plays certain carrier function to the nanoscale manganese dioxide particle, can prevent the reunion of manganese dioxide semi-conductor nano particles, and can control the size and the distribution of manganese dioxide semi-conductor nano particles and improve stability.
Composite membrane of the present invention is good to the electrode catalyst performance, and 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 3.85%, 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 is mutually compound with conductive substrates with the form of film with the manganese dioxide semi-conductor nano particles, make that have high-energy-density, aboundresources, eco-friendly manganese dioxide semiconductor nano material is put to practical application with form of film, avoid the reunion of nano particle, shown superior chemical property.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 AFM pattern phenogram of the composite membrane that is used for DSSC that obtains of embodiment 15 to electrode (manganese dioxide/polythiophene composite film is to electrode); Fig. 3 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 to electrode from the bottom to top successively by being formed by connecting under conductive substrates (1), manganese dioxide membrane (2) and the acting in conjunction of conducting polymer thin film (3) by active force between intermolecular force and atom.
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 3.85%, 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 manganese dioxide membrane (2) is 6～10 μ m, and the thickness of conducting polymer thin film (3) is 2～4 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 conducting polymer is polypyrrole, poly-(1-C
1-7The alkyl pyrroles), poly-(3-C
1-8The alkyl pyrroles), polythiophene, 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, two or three.
Embodiment five: present embodiment such as the embodiment one described preparation method who is used for the composite membrane of DSSC to electrode, realize by following steps:
One, electrophoretic deposition prepares manganese dioxide membrane
The configuration of a, manganese dioxide electrophoresis liquid: manganese dioxide powder is dispersed in the aprotic organic solvent, and then adding TBAH, stir after 24 hours, left standstill 1 hour, centrifugal then, again manganese dioxide powder is scattered in the aprotic organic solvent after the drying, then sonic oscillation 20～40min, leave standstill 20～40min again, obtain the manganese dioxide electrophoresis liquid of stable suspension; The proportionate relationship that wherein said twice manganese dioxide is scattered in aprotic organic solvent is: the ratio of manganese dioxide quality and aprotic organic solvent volume is 6～7g: 350mL, and the ratio of manganese dioxide quality and TBAH volume is 6～7g: 150mL;
The preparation of b, manganese dioxide membrane: in the manganese dioxide 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 3～5 seconds deposits manganese dioxide membrane on conductive substrates, the conductive substrates that will deposit manganese dioxide membrane then obtains manganese dioxide membrane at 70 ℃～90 ℃ following vacuumize 3～5h on conductive substrates;
Two, composite membrane is to the preparation of electrode
The configuration of a, conducting polymer monomer electrodeposit liquid: the conducting polymer monomer is dissolved in obtains conducting polymer monomer electrodeposit liquid in the BFEE, the concentration of conducting polymer monomer is 15～20mmol/L;
B, composite membrane is to the preparation of electrode: in conducting polymer monomer electrodeposit liquid, with the sweep speed is 0.05V/s, with electrochemical workstation with three-electrode system, with the conductive substrates that deposits manganese dioxide membrane 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 manganese dioxide/conductive polymer composite film to electrode at 70 ℃～90 ℃ following vacuumize 10～15h again, the composite membrane that promptly is used for DSSC is to electrode.
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 six: present embodiment and embodiment five are different is that the preparation method of manganese dioxide powder is in a step of step 1: potassium permanganate and manganese sulfate are dissolved in respectively to be configured to mass concentration in the deionized water be the liquor potassic permanganate of 16g/L and the manganese sulfate solution of 152g/L, measure the 60mL liquor potassic permanganate then and place three-necked bottle, and then add 15mL NH
3H
2O, regulating the pH value is 10～11, stir, and the speed with 10/min when stirring drips manganese sulfate solution 10mL in three-necked bottle, continue stirring reaction 8～12h after dripping again, leave standstill 20～40min then, remove supernatant liquor, then with lower sediment thing suction filtration, and with ethanol the sediment filter cake is taken out and to be washed 3～5 times, again with sediment at 70～90 ℃ of down dry 20～24h, then sediment is ground to form the powder that particle diameter is 1～10 μ m, at 360～420 ℃ of following calcination 3h, promptly obtain manganese dioxide powder again.Other step and parameter are identical with embodiment five.
Embodiment seven: present embodiment is different with embodiment five or six 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 five or six.
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
3SO
3, [EMIm] BF
4Perhaps [EMIm] PF
6, wherein [EMIm] is 1-ethyl-3-methylimidazole cation).Ethers is dimethoxymethane or 1,2-dimethoxy ethane.
Embodiment eight: present embodiment and embodiment five, six or seven 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 five, six or seven.
Conducting metal described in the present embodiment is copper, nickel, zinc, titanium or tin.
Embodiment nine: present embodiment and embodiment five to eight are different is that electrophoresis time is 4 seconds in the b step of step 1.Other step and parameter are identical with embodiment five to eight.
Embodiment ten: present embodiment and embodiment five to nine are different is that the conducting polymer monomer is pyrroles, azole derivatives, thiophene or thiophene derivant in a step of step 2, and described azole derivatives is 1-C
1-7Alkyl pyrroles or 3-C
1-8The alkyl pyrroles, described thiophene derivant is 3-C
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 five to nine.
Pyrroles and azole derivatives conducting polymer monomer are by the terraced uncommon Industrial Co., Ltd's production of liking to change into of Japan in the present embodiment, and thiophene and thiophene derivant conducting polymer monomer are that effluent south Puyang Huicheng Chemicals Co., Ltd or Japanese TCI change into the production of industrial (Shanghai) Co., Ltd..
Embodiment 11: present embodiment and embodiment five to ten are different is that the conducting polymer described in the b step of step 2 is polypyrrole, poly-(1-C
1-7The alkyl pyrroles), poly-(3-C
1-8The alkyl pyrroles), polythiophene, 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 steps and parameter are identical with embodiment five to ten.
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 |
| Manganese dioxide/polythiophene | 15? | 10 circles | 3.85％? |
| Manganese dioxide/poly-(3-ethylthiophene) | 10? | 10 circles | 3.25％? |
| Manganese dioxide/poly-(3-phenyl thiophene) | 15? | 15 circles | 3.10％? |
| Manganese dioxide/poly-(3-ethanol based thiophene) | 10? | 15 circles | 3.30％? |
| Manganese dioxide/poly-(3,4-ethylene group dioxy thiophene) | 10? | 15 circles | 3.77％? |
| Manganese dioxide/poly-(3, the 4-dimethoxy-thiophene) | 15? | 15 circles | 3.61％? |
| Manganese dioxide/polypyrrole | 10? | 15 circles | 3.65％? |
| Manganese dioxide/poly-1-N-ethyl pyrrole N- | 20? | 20 circles | 3.32％? |
| Manganese dioxide/poly-3-butyl pyrroles | 15? | 25 circles | 3.20％? |
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 3.85%, it can reach the photoelectric conversion efficiency to the dye sensitization of solar of electrode based on Pt.
Embodiment 12: present embodiment and embodiment five to 11 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 five to 11.
Embodiment 13: present embodiment and embodiment five 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 manganese dioxide membrane
The configuration of a, manganese dioxide electrophoresis liquid: 0.6～0.7g manganese dioxide powder is dispersed in the 35mL acetonitrile solvent, and then adding 15mL TBAH, stir after 24 hours, left standstill 1 hour, centrifugal then, again manganese dioxide powder is scattered in after the drying in the 35mL acetonitrile solvent, then sonic oscillation 30min, leave standstill 30min again, obtain the manganese dioxide electrophoresis liquid of stable suspension;
The preparation of b, manganese dioxide membrane: in the manganese dioxide electrophoresis liquid, with conductive substrates as anode, platinum electrode is as negative electrode, negative electrode and anode spacing are from 1.0cm, under direct current 50V voltage, electrophoresis 4 seconds deposits manganese dioxide membrane on conductive substrates, the conductive substrates that will deposit manganese dioxide membrane then obtains manganese dioxide membrane at 80 ℃ of following vacuumize 4h on conductive substrates;
Two, composite membrane is to the preparation of electrode
The configuration of a, thiophene electrodeposit liquid: thiophene monomer is dissolved in obtains conducting polymer monomer electrodeposit liquid in the BFEE, the concentration of thiophene monomer is 15～20mmol/L;
B, composite membrane is to the preparation of electrode: in the thiophene monomer electrodeposit liquid, with the sweep speed is 0.05V/s, with electrochemical workstation with three-electrode system, with the conductive substrates that deposits manganese dioxide membrane as work electrode, the platinum electrode conduct is to electrode, saturated calomel 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 15 circles, take out work electrode then, use deionized water rinsing, obtain manganese dioxide/conductive polymer 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 five.
Present embodiment is carried out atomic force microscope (AFM) to the composite membrane that is used for DSSC that obtains to electrode (manganese dioxide/polythiophene composite film is to electrode) and is characterized, and the result as shown in Figure 2.Can be seen that by Fig. 2 the manganese dioxide/polythiophene composite film that obtains is the particle membrane of continuous even compact to electrode, 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 (manganese dioxide/polythiophene composite film is to electrode), then will be based on the manganese dioxide/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 shows that the photoelectric conversion efficiency height is 3.85%, short-circuit current density is 9.551mA/cm
2, open circuit voltage is 0.762mV, the composite membrane that is used for DSSC of present embodiment is to the excellent catalytic effect of electrode (manganese dioxide/polythiophene composite film is to electrode).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 shows, is 5.168% based on existing Pt to the electricity conversion of the DSSC of electrode, based on the manganese dioxide/polythiophene composite film of present embodiment to the photoelectric conversion efficiency of the DSSC of electrode 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 (manganese dioxide/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 3.As shown in Figure 3, the manganese dioxide/polythiophene composite film of present embodiment is good to the electrochemical reversibility of electrode, stable electrochemical property.
Claims (6)
1. preparation method who is used for the composite membrane of DSSC to electrode, the described composite membrane that is used for DSSC to electrode from the bottom to top successively by being formed by connecting under conductive substrates (1), manganese dioxide membrane (2) and the acting in conjunction of conducting polymer thin film (3) by active force between intermolecular force and atom; 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 manganese dioxide membrane
A, the configuration of manganese dioxide electrophoresis liquid: manganese dioxide powder is dispersed in the aprotic organic solvent, and then adding TBAH, stir after 24 hours, left standstill 1 hour, centrifugal then, again manganese dioxide powder is scattered in the aprotic organic solvent after the drying, sonic oscillation 20～40min then, leave standstill 20～40min again, obtain the manganese dioxide electrophoresis liquid of stable suspension, wherein twice manganese dioxide powder proportionate relationship of being scattered in aprotic organic solvent is: the ratio of manganese dioxide powder quality and aprotic organic solvent volume is 6～7g: 350mL, and the ratio of manganese dioxide powder quality and TBAH volume is 6～7g: 150mL;
The preparation of b, manganese dioxide membrane: in the manganese dioxide 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 3～5 seconds deposits manganese dioxide membrane on conductive substrates, the conductive substrates that will deposit manganese dioxide membrane then obtains manganese dioxide membrane at 70 ℃～90 ℃ following vacuumize 3～5h on conductive substrates;
Two, composite membrane is to the preparation of electrode
The configuration of a, polymer monomer electrodeposit liquid: the conducting polymer monomer is dissolved in obtains conducting polymer monomer electrodeposit liquid in the BFEE, the concentration of conducting polymer monomer is 15～20mmol/L;
B, composite membrane is to the preparation of electrode: in conducting polymer monomer electrodeposit liquid, with the sweep speed is 0.05V/s, with electrochemical workstation with three-electrode system, with the conductive substrates that deposits manganese dioxide membrane 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 manganese dioxide/conductive polymer composite film to electrode at 70 ℃～90 ℃ following vacuumize 10～15h again, the composite membrane that promptly is used for DSSC is to electrode.
2. a kind of preparation method who is used for the composite membrane of DSSC to electrode according to claim 1, the preparation method who it is characterized in that manganese dioxide powder in a step of step 1 is: potassium permanganate and manganese sulfate are dissolved in respectively to be configured to mass concentration in the deionized water be the liquor potassic permanganate of 16g/L and the manganese sulfate solution of 152g/L, measure the 60mL liquor potassic permanganate then and place three-necked bottle, and then add 15mL NH
3H
2O, regulating the pH value is 10～11, stir, and the speed with 10/min when stirring drips manganese sulfate solution 10mL in three-necked bottle, continue stirring reaction 8～12h after dripping again, leave standstill 20～40min then, remove supernatant liquor, then with lower sediment thing suction filtration, and with ethanol the sediment filter cake is taken out and to be washed 3～5 times, again with sediment at 70～90 ℃ of down dry 20～24h, then sediment is ground to form the powder of particle diameter at 1～10 μ m, at 360～420 ℃ of following calcination 3h, promptly obtain manganese dioxide powder again.
3. a kind of preparation method who is used for the composite membrane of DSSC to electrode according to claim 1 and 2 is characterized in that aprotic organic solvent is acetonitrile, acetone, carbonic ester, glyoxaline ion liquid or ethers in a step of step 1.
4. a kind of preparation method who is used for the composite membrane of DSSC to electrode according to claim 3 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.
5. a kind of preparation method who is used for the composite membrane of DSSC to electrode according to claim 1 and 2 is characterized in that in the step 1 in the b step electrophoresis 4 seconds.
6. a kind of preparation method who is used for the composite membrane of DSSC to electrode according to claim 5, it is characterized in that the conducting polymer monomer is pyrroles, azole derivatives, thiophene or thiophene derivant in a step of step 2, described azole derivatives is 1-C
1-7Alkyl pyrroles or 3-C
1-8The alkyl pyrroles, described thiophene derivant is 3-C
1-12Alkylthrophene, 3-phenyl thiophene, 3-ethanol based thiophene, 3,4-ethylene group dioxy thiophene or 3,4-dimethoxy-thiophene.
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| CN108630340B (en) * | 2017-03-22 | 2020-06-26 | 北京赛特超润界面科技有限公司 | Preparation method of PEDOT (Poly ethylene terephthalate): PSS (Polytetrafluoroethylene) @ ionic liquid gel composite self-supporting flexible transparent electrode |
| CN109065895A (en) * | 2018-07-26 | 2018-12-21 | 北京化工大学常州先进材料研究院 | The preparation of iron cobalt codope carbon nitrogen core-shell particles material and its application in terms of electro-catalysis |
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