Method for preparing co-sensitized TiO2 photo-anode through acoustic resonance reinforcement, anode and device

Abstract

The invention discloses a method for preparing a co-sensitized TiO2 photo-anode through acoustic resonance reinforcement, the anode and a device. The titanium dioxide photo-anode is dye-sensitized in an acoustic resonance mode; the acceleration of acoustic resonance is 196-980 m / s < 2 >, and the dye sensitization time is 5-10 minutes; dye used for dye sensitization is ruthenium dye N749 and organic dye CZD, CS1, CS2 or CS3. The method mainly comprises the following steps: (1) placing a titanium dioxide photo-anode in a mixed solution of ruthenium dye and organic dye; (2) starting the acoustic resonator, and adjusting the acceleration and operation time of the acoustic resonator; and (3) washing, drying, assembling, injecting electrolyte, sealing and the like to prepare the co-sensitized solar cell device. According to the method, the co-sensitized solar cell is rapidly prepared through acoustic resonance reinforcement, the preparation time is greatly shortened, the photoelectric conversion efficiency of the method is superior to that of a traditional immersion bath mode, and the method has good application prospects.

Description

Technical Field

[0001] The present invention belongs to the field of optoelectronic device preparation, and particularly relates to a method for preparing a co-sensitized TiO 2 photoanode by acoustic resonance enhancement, an anode and a device. Background Art

[0002] In 1991, a breakthrough was made in the field of dye-sensitized solar cells (DSSCs). O'Regan and used a ruthenium-bipyridine complex dye (N3) and a high-surface-area TiO 2 thin film, thereby increasing the dye loading and photocurrent density. The team subsequently developed some more efficient photosensitizing dyes, such as N719, with a photoelectric conversion efficiency of 11.1%, and the black dye (N749) also had a photoelectric conversion efficiency exceeding 10%. In addition, the C101 dye developed by the Wang Peng team had a photoelectric conversion efficiency of 11.4%. Since the adsorption of a single dye on the TiO 2 surface will leave gaps, especially for relatively large molecules such as ruthenium dyes. These gaps increase the probability of recombination of injected electrons with the electrolyte, resulting in less than ideal optoelectronic performance of the device. Therefore, a co-sensitization strategy can be adopted, that is, a co-sensitization method using a mixed solution of ruthenium dye and organic dye, allowing relatively small organic molecules to fill the gaps between ruthenium dye molecules. Usually, the performance of the co-sensitized device will also be improved.

[0003] The preparation process of the co-sensitized solar cell device is as follows: The TiO 2 photoanode is sensitized in a mixed dye of ruthenium dye and organic dye, then assembled with a counter electrode, filled with an electrolyte, and then encapsulated. Among them, the time for immersing the TiO 2 photoanode in the dye solution for sensitization usually reaches more than ten hours to 24 hours. Therefore, the rapid sensitization of the photoanode has become a bottleneck problem restricting the low-cost manufacturing and large-scale production of co-sensitized solar cells.

[0004] On the other hand, acoustic resonance, as a new type of high-efficiency mixing technology, its working principle is based on the coupling of vibrational macro mixing and acoustic streaming micro mixing. This technology can not only achieve uniform dispersion of the mixed materials throughout the field through large-scale mixing and micro mixing, but also avoid physical damage to the mixed materials or the occurrence of dangerous accidents caused by the shear of the impeller or friction and collision with the wall surface. Therefore, this mixing method is widely used for sensitive substances, such as the mixing of explosives. Recently, acoustic resonance technology has been extended to the synthesis field, which does not require a large amount of solvents and stirring paddles or grinding media. So far, this technology has been used in the synthesis of co-crystals, metal-organic frameworks, and metal-catalyzed coupling reactions. Summary of the Invention

[0005] The object of the present invention is to provide a method for preparing a co-sensitized TiO 2 photoanode, an anode and a device. By using acoustic resonance enhancement, the sensitization time can be significantly shortened (from more than 10 hours to 5-10 minutes), so as to realize the rapid preparation of co-sensitized solar cells. At the same time, the photoelectric conversion efficiency of the co-sensitized device prepared by this method has also been improved (from 7.18% to 7.89%). Therefore, this method has the prospect of industrial application.

[0006] To achieve the above object, the technical solutions adopted by the present invention include:

[0007] A method for preparing a co-sensitized TiO 2 photoanode by acoustic resonance enhancement, which dyes the titanium dioxide photoanode by acoustic resonance;

[0008] The acceleration of the acoustic resonance is 196-980 m / s 2 , and the dye sensitization time is 5-10 minutes;

[0009] The dyes used for dye sensitization are ruthenium dye N749 and organic dyes CZD, CS1, CS2 or CS3.

[0010] Optionally, the solution concentration of the ruthenium dye N749 is 0.3 mM, the concentration of the organic dyes CZD, CS1, CS2 or CS3 is 0.05 mM, and the solvent is tert-butanol / acetonitrile with a volume ratio of 1 / 1.

[0011] Optionally, the acceleration of the acoustic resonance is 196 m / s 2 , and the dye sensitization time is 5 minutes.

[0012] Optionally, the acceleration of the acoustic resonance is 490 m / s 2 , and the dye sensitization time is 5 minutes.

[0013] Optionally, the acceleration of the acoustic resonance is 980 m / s 2 , and the dye sensitization time is 5 minutes.

[0014] Optionally, the acceleration of the acoustic resonance is 490 m / s 2 , and the dye sensitization time is 7 minutes.

[0015] Optionally, the acceleration of the acoustic resonance is 490 m / s 2 , and the dye sensitization time is 10 minutes.

[0016] A co-sensitized TiO 2 photoanode, and the co-sensitized TiO 2 photoanode is prepared by using the acoustic resonance enhancement method for preparing co-sensitized TiO according to any one of the present invention2 It is prepared by the method of the photoanode.

[0017] A DSSC device, wherein the TiO of the DSSC device 2 The photoanode is the co-sensitized TiO described in the present invention 2 Photoanode.

[0018] Optionally, the electrolyte solution used in the preparation of the DSSC device has the following composition: 0.6 mol / L 1,2-dimethyl-3-propylimidazolium iodide, 0.1 mol / L LiI, 0.05 mol / L I 2 , and an acetonitrile solution of 0.3 mol / L 4-tert-butylpyridine.

[0019] Advantages of the present invention:

[0020] The method for rapidly preparing a co-sensitized solar cell by acoustic resonance enhancement of the present invention has: Advantage 1: The co-sensitization time is greatly shortened by using acoustic resonance enhancement (shortened from more than 10 hours to 5-10 minutes); Advantage 2: The photoelectric conversion efficiency of the co-sensitized device can be improved by using acoustic resonance enhancement (increased from 7.18% to 7.89%). Specific embodiments

[0021] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. The following examples are exemplary and are only used to explain the present invention and should not be construed as limiting the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0022] The method for rapidly preparing a co-sensitized solar cell by acoustic resonance enhancement provided by the present invention includes the following steps:

[0023] (1) Place the titanium dioxide photoanode in a mixed solution of ruthenium dye and organic dye;

[0024] (2) Start the acoustic resonance instrument and adjust the acceleration (196-980 m / s 2 ) and running time (5-10 minutes) of the acoustic resonance instrument;

[0025] (3) Prepare the co-sensitized solar cell through processes such as washing, drying, assembling, injecting electrolyte, and sealing.

[0026] The method is to rapidly co-sensitize the titanium dioxide photoanode by acoustic resonance, and its area is 0.16 cm 2 .

[0027] The acceleration of the acoustic resonance instrument of the method is 196 - 980 m / s 2 , and the co-sensitization time is 5 - 10 min.

[0028] In the mixed solution of ruthenium dye and organic dye of the method, the ruthenium dye is N749 with a concentration of 0.3 mM, the organic dye is CZD (structure see ZL 202111215229.3), CS1, CS2 or CS3 (structure see 《Solar Energy》2021, 230, 312 - 320.) with a concentration of 0.05 mM, and the solvent is tert-butanol / acetonitrile (volume ratio 1 / 1); the electrolyte composition is: 0.6 mol / L 1,2-dimethyl-3-propylimidazolium iodide, 0.1 mol / L LiI, 0.05 mol / L I 2 , and 0.3 mol / L acetonitrile solution of 4-tert-butylpyridine. The assembly, preparation and testing methods of the co-sensitized device can be referred to ZL 201911223406.5.

[0029] Example 1:

[0030] (1) Place the titanium dioxide photoanode in the mixed solution of ruthenium dye and organic dye. The ruthenium dye is N749 with a concentration of 0.3 mM, the organic dye is CZD with a concentration of 0.05 mM, and the solvent is tert-butanol / acetonitrile (volume ratio 1 / 1);

[0031] (2) Adjust the acceleration of the acoustic resonance instrument to 196 m / s 2 , and the sensitization time is 5 minutes;

[0032] (3) Prepare the co-sensitized solar cell device through processes such as washing, drying, assembling, injecting electrolyte and sealing. Under the standard simulated sunlight intensity, its photoelectric conversion efficiency is measured to be 7.36% (short-circuit current density is 15.4 mA / cm 2 , open-circuit voltage is 742 mV, and fill factor is 64.4%).

[0033] Example 2:

[0034] In step (1), the organic dye is CS1, and the rest is the same as Example 1. The co-sensitized solar cell device is prepared. Under the standard simulated sunlight intensity, its photoelectric conversion efficiency is measured to be 7.20% (short-circuit current density is 15.3 mA / cm 2 , open-circuit voltage is 736 mV, and fill factor is 63.9%).

[0035] Example 3:

[0036] In step (1), the organic dye is CS2. For the rest of Example 1, a co-sensitized solar cell device is prepared, and its photoelectric conversion efficiency is measured to be 7.28% (short-circuit current density is 15.3 mA / cm 2 , open-circuit voltage is 738 mV, and fill factor is 64.5%) under standard simulated sunlight intensity.

[0037] Example 4:

[0038] In step (1), the organic dye is CS3. For the rest of Example 1, a co-sensitized solar cell device is prepared, and its photoelectric conversion efficiency is measured to be 7.24% (short-circuit current density is 15.3 mA / cm 2 , open-circuit voltage is 740 mV, and fill factor is 63.9%) under standard simulated sunlight intensity.

[0039] Example 5:

[0040] In step (2), the acceleration of the acoustic resonance instrument is adjusted to 490 m / s 2 , and the rest is the same as Example 1. A co-sensitized solar cell device is prepared, and its photoelectric conversion efficiency is measured to be 7.73% (short-circuit current density is 15.9 mA / cm 2 , open-circuit voltage is 753 mV, and fill factor is 64.6%) under standard simulated sunlight intensity.

[0041] Example 6:

[0042] In step (2), the acceleration of the acoustic resonance instrument is adjusted to 980 m / s 2 , and the rest is the same as Example 1. A co-sensitized solar cell device is prepared, and its photoelectric conversion efficiency is measured to be 7.64% (short-circuit current density is 15.8 mA / cm 2 , open-circuit voltage is 750 mV, and fill factor is 64.5%) under standard simulated sunlight intensity.

[0043] Example 7:

[0044] In step (2), the acceleration of the acoustic resonance instrument is adjusted to 490 m / s 2 , the sensitization time is 7 minutes, and the rest is the same as Example 1. A co-sensitized solar cell device is prepared, and its photoelectric conversion efficiency is measured to be 7.89% (short-circuit current density is 16.1 mA / cm 2 , open-circuit voltage is 758 mV, and fill factor is 64.7%) under standard simulated sunlight intensity.

[0045] Example 8:

[0046] In step (2), the acceleration of the acoustic resonance instrument is adjusted to 490 m / s 2, with a sensitization time of 10 minutes, and the rest the same as in Example 1, a co-sensitized solar cell device was prepared, and its photoelectric conversion efficiency was measured to be 7.69% under standard simulated sunlight intensity (short-circuit current density was 15.8 mA / cm 2 , open-circuit voltage was 754 mV, and fill factor was 64.6%).

[0047] To compare the differences between co-sensitization and single ruthenium dye N749 sensitization under acoustic resonance enhancement conditions, we also conducted experiments under the condition of single sensitization with ruthenium dye N749 (concentration of ruthenium dye N749 was 0.3 mM, solvent was tert-butanol / acetonitrile (volume ratio 1 / 1), and the acceleration of the acoustic resonance instrument was 196 m / s 2 , and the sensitization time was 5 min) for comparison. The photoelectric conversion efficiency of the obtained sensitized device under standard simulated sunlight intensity was 7.02% (short-circuit current density was 14.6 mA / cm 2 , open-circuit voltage was 724 mV, and fill factor was 66.4%). It can be seen that both the short-circuit current density and open-circuit voltage of the organic dye co-sensitized device have been improved. The reason may be that the organic dye broadens the absorption spectral band range of the device, and in addition, it can effectively inhibit the recombination of injected electrons and electrolytes, ultimately improving the photoelectric conversion efficiency of the device.

[0048] To compare the differences between acoustic resonance enhanced co-sensitization and traditional immersion sensitization, some experiments under immersion conditions were also conducted for comparison, and the photoelectric performance data of the obtained co-sensitized devices under standard simulated sunlight intensity are listed in Table 1:

[0049] The titanium dioxide photoanode was placed in the dye solution and immersed for 12 - 24 hours in the dark. After washing, drying, assembling, injecting electrolyte, and sealing, etc., co-sensitized devices were prepared. Similarly, the dye was ruthenium dye N749 with a concentration of 0.3 mM, the organic dye was CZD with a concentration of 0.05 mM, and the solvent was tert-butanol / acetonitrile (volume ratio 1 / 1); while the composition of the electrolyte was: 0.6 mol / L 1,2-dimethyl-3-propylimidazolium iodide, 0.1 mol / L LiI, 0.05 mol / L I 2 , and 0.3 mol / L acetonitrile solution of 4-tert-butylpyridine.

[0050] Table 1 Data table of different sensitization times and device performance under traditional immersion method

[0051]

[0052] It can be seen that under the traditional immersion method, the photoelectric conversion efficiency of the device is the highest (No. 2) when the sensitization time is 16 hours, reaching 7.18%. Further extending the sensitization time, the photoelectric conversion efficiency of the device decreases instead, probably because the dye aggregates and agglomerates on the surface of titanium dioxide (No. 3 and No. 4).

[0053] It can be seen that by adopting the acoustic resonance enhancement technology, the sensitization time of the dye-sensitized solar cell can be significantly shortened (from more than 10 hours to 5-10 minutes). At the same time, the photoelectric conversion efficiency of the co-sensitized device is also improved (from 7.18% to 7.89%). The reason may be that in the co-sensitization by the acoustic resonance method, the ruthenium dye organic dye can be adsorbed more densely and orderly on the surface of titanium dioxide under the action of supergravity.

[0054] It can be understood that the above embodiments are only for illustrating the preferred embodiments of the present invention, but the invention is not limited thereto. For those of ordinary skill in the art, various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these modifications and improvements also fall within the protection scope of the present invention.

Claims

1. A method for preparing a co-sensitized TiO2 photoanode by acoustic resonance enhancement, characterized in that: The titanium dioxide photoanode was dye-sensitized by acoustic resonance; The acceleration of the acoustic resonance is 196-980 m / s 2 , the dye sensitization time is 5 to 10 minutes; The dyes used for dye sensitization are ruthenium dye N749 and organic dyes CZD, CS1, CS2 or CS3.

2. The method for preparing a co-sensitized TiO2 photoanode by acoustic resonance enhancement according to claim 1 or 2, characterized in that: The solution concentration of the ruthenium dye N749 is 0.3 mM, the concentration of the organic dye CZD, or CS1, or CS2, or CS3 is 0.05 mM, and the solvent is tert-butanol / acetonitrile in a volume ratio of 1 / 1.

3. The method for preparing a co-sensitized TiO2 photoanode by acoustic resonance enhancement according to claim 1 or 2, characterized in that: The acceleration of the acoustic resonance is 196m / s 2 , the dye sensitization time was 5 minutes.

4. The method for preparing a co-sensitized TiO2 photoanode by acoustic resonance enhancement according to claim 1 or 2, characterized in that: The acceleration of the acoustic resonance is 490m / s 2 , the dye sensitization time was 5 minutes.

5. The method for preparing a co-sensitized TiO2 photoanode by acoustic resonance enhancement according to claim 1 or 2, characterized in that: The acceleration of the acoustic resonance is 980m / s 2 , the dye sensitization time was 5 minutes.

6. The method for preparing a co-sensitized TiO2 photoanode by acoustic resonance enhancement according to claim 1 or 2, characterized in that: The acceleration of the acoustic resonance is 490m / s 2 , the dye sensitization time was 7 minutes.

7. The method for preparing a co-sensitized TiO2 photoanode by acoustic resonance enhancement according to claim 1 or 2, characterized in that: The acceleration of the acoustic resonance is 490m / s 2 , the dye sensitization time was 10 min.

8. A co-sensitized TiO2 photoanode, characterized in that: The co-sensitized TiO2 photoanode is prepared by the method for preparing the co-sensitized TiO2 photoanode by acoustic resonance enhancement as described in any one of claims 1 to 7.

9. A DSSC device, characterized in that: The TiO2 photoanode of the DSSC device is the co-sensitized TiO2 photoanode described in claim 8.

10. The DSSC device according to claim 9, characterized in that The electrolyte solution used in the preparation of the DSSC device is composed of an acetonitrile solution of 0.6 mol / L 1,2-dimethyl-3-propyl imidazole iodide, 0.1 mol / L LiI, 0.05 mol / L I2, and 0.3 mol / L 4-tert-butylpyridine.

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