CN110797464B - Method for recycling transparent conductive electrode of organic solar cell - Google Patents
Method for recycling transparent conductive electrode of organic solar cell Download PDFInfo
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Images
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
- H10K30/82—Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
-
- 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
- Y02E10/549—Organic PV cells
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/20—Waste processing or separation
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/82—Recycling of waste of electrical or electronic equipment [WEEE]
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- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Manufacturing & Machinery (AREA)
- Photovoltaic Devices (AREA)
Abstract
A method for recycling transparent conductive electrodes of organic solar cells is characterized by comprising the following steps: the method specifically comprises the steps of placing a waste organic photovoltaic device in an organic solvent to remove a top electrode, an interface material and a photoactive layer of the device, then placing the device in a dilute acid solution to remove residual metal electrodes and interface materials, so as to obtain a recyclable metal oxide type transparent conductive electrode, and then taking the recycled metal oxide type transparent conductive electrode as a bottom electrode to prepare the organic photovoltaic device. The method for recycling the metal oxide type transparent conductive electrode from the used photovoltaic device for multiple times solves the problems of indium scarcity and high price in the ITO, avoids the re-preparation of the bottom electrode, and reduces the material cost and the preparation cost; under the same preparation condition, the prepared battery device has photoelectric conversion efficiency higher than that of the device under the first use condition, and the stability of the battery device is not influenced.
Description
Technical Field
The invention belongs to the technical field of organic photovoltaic cell devices, and particularly relates to a method for recycling a transparent conductive electrode of an organic photovoltaic device.
Background
The polymer solar cell has unique advantages in the aspects of wet processing, large area and flexibility as a novel energy device. Recently, polymer solar cells have made important breakthrough in energy conversion, and the efficiency of such cells has been reported to break 16%, which represents a good application trend. However, there are still large gaps in the photoelectric conversion efficiency, the stability of the device and the service life of the polymer solar cell compared to the commercialized silicon-based solar cell. Therefore, in order to expand its application, in addition to enhancing the research work in these three aspects, work should be carried out in the optimization and cost control of device fabrication. In a traditional polymer solar cell device, an optical active layer material (such as PBDBT-2F: IT-4F and the like) and a transparent conductive electrode (such as ITO, FTO and the like) are two main factors for leading the cost of the device, and the cost of the two factors can be controlled well so as to effectively improve the competitive power of the polymer solar cell.
The metal oxide type transparent conductive electrode is often used as a bottom electrode of an organic photoelectric device because of its good light transmittance and conductivity. However, the preparation cost is expensive (for example, indium in ITO is a rare metal, and ITO, FTO, and AZO metal oxide type transparent conductive electrodes are commonly prepared by magnetron sputtering). Therefore, it has been attempted to replace the metal oxide type transparent conductive electrode with a conductive polymer, a nano metal wire, graphene, a metal mesh, or the like, and although good results have been obtained, there is a certain difference in device performance compared to the metal oxide type transparent conductive electrode. Therefore, from the perspective of recycling the metal oxide type transparent conductive electrode, the interface material, the active layer and the metal electrode are removed from the discarded organic photovoltaic device, so as to obtain the recyclable metal oxide type transparent conductive electrode with excellent performance, and reduce the preparation cost of the organic solar cell, which is an effective way to solve the above problems.
Disclosure of Invention
The invention aims to improve the recycling efficiency of a metal oxide type transparent conductive electrode, provide a new idea for reducing and improving the preparation cost of an organic solar cell, and provide a method for recycling the metal oxide type transparent conductive electrode of the organic solar cell.
The purpose of the invention is realized according to the following technical scheme:
a method for recycling transparent conductive electrodes of organic solar cells is characterized by comprising the following steps: the method comprises the following steps of putting a waste organic photovoltaic device into an organic solvent to remove a metal top electrode, an upper interface layer and a light activity layer of the device, then putting the device into a dilute weak acid aqueous solution to remove a residual metal top electrode and a residual lower interface layer, so as to obtain a recyclable metal oxide type transparent conductive electrode, and then taking the recycled metal oxide type transparent conductive electrode as a bottom electrode to prepare the organic photovoltaic device; the organic photovoltaic device comprises a solar cell with an active layer made of organic polymer or an organic conjugated micromolecule solar cell, wherein the organic polymer is P3HT PCBM, PBDB-T-2F IT-4F, PTB7 PC71BM or PPV, CdTe, etc. and the conjugated small molecule is CuPc-PCBM or DR3TBDT 2T-PC71BM, etc.; the transparent conductive electrode comprises an indium tin oxide conductive electrode, a fluorine-doped tin dioxide conductive electrode or an aluminum-doped zinc oxide conductive electrode; the lower interface layer comprises ZnO and TiO2、SnO2、PEDOT:PSS、MoO3、Ag2O, NiO, respectively.
Further, the organic solvent is one of chloroform, o-dichlorobenzene, chlorobenzene, carbon disulfide and the like.
Further, the volume concentration of the dilute weak acid aqueous solution is 1-5%.
Further, the weak acid in the dilute weak acid aqueous solution is one or more of lactic acid, acetic acid, propionic acid, boric acid, phytic acid, oxalic acid and other weak acids.
Preferably, the dilute weak acid aqueous solution is a mixed weak acid aqueous solution prepared by mixing lactic acid and acetic acid according to a volume ratio of 1: 1.
A method for recycling a transparent conductive electrode of an organic solar cell is characterized by comprising the following steps:
(1) placing the waste organic photovoltaic device in a solvent capable of dissolving the material of the photoactive layer, and fully removing the photoactive layer, an upper interface layer and a metal top electrode thereof under the ultrasonic oscillation condition;
(2) after the step (1), placing the transparent conductive electrode with a part of metal top electrode and a lower interface layer left on the surface in a dilute acid aqueous solution with the volume concentration of 1-5%, and performing ultrasonic cleaning until the surface of the transparent conductive electrode is clean, wherein the metal top electrode comprises but is not limited to Al, Ag or Ca and the like, and the lower interface layer comprises but is not limited to ZnO, TiO and the like2、SnO2PEDOT, PSS or PFN, etc.;
(3) placing the recovered metal oxide type transparent conductive electrode in deionized water containing a small amount of detergent for ultrasonic cleaning for 10-15 minutes, and gently rubbing the transparent conductive electrode to remove impurities such as grease, dust, dirt, ions and the like on the surface; then placing the mixture in deionized water for ultrasonic cleaning for 10-15 minutes; then respectively placing the recovered conductive glass electrodes in acetone, absolute ethyl alcohol, chloroform and isopropanol solutions in sequence, ultrasonically cleaning for 10-15 minutes, placing the cleaned electrodes in a drying oven, and drying for later use at the drying temperature of 80-90 ℃ for 20-30 minutes;
(4) the recovered transparent conductive electrode is taken as a bottom electrode, and a lower interface layer, an optical active layer, an upper interface layer and a metal top electrode are sequentially prepared on the bottom electrode;
(5) and (4) repeating the steps (1) - (4) when the recycling and reusing are carried out again.
In the preparation process, under the ultrasonic oscillation condition, organic solvent or acid is easy to decompose and then permeate into the transparent conductive electrode, so that the microstructure on the surface of the recovered transparent conductive electrode is damaged, the performance is influenced, and when the transparent conductive electrode is repeatedly used as a bottom electrode, the photoelectric conversion efficiency is low, the stability is poor, and the conductivity is seriously attenuated. The organic solvent and the weak acid are reasonably selected to act on the specific active layer and the lower interface layer, and the organic solvent and the weak acid are combined to act on the lower interface layer and the surface of the transparent conductive electrode together, so that the complete transparent conductive electrode is successfully recovered; particularly, the invention further adjusts and optimizes the surface microstructure of the recovered transparent conductive electrode, reduces the surface roughness of the transparent conductive electrode, enhances the occlusion capacity of the surface and the interface layer, ensures that the binding force of the interface layer prepared again and the recycled bottom electrode is better, and transmits layer by layer, so that the uniformity of the prepared interface layer, the active layer and the electrode layer is optimized, and further improves the photoelectric conversion efficiency and the performance stability of the electrode layer.
The invention has the following beneficial effects:
the method for recycling the metal oxide type transparent conductive electrode from the used photovoltaic device for multiple times solves the problems of rare indium and high price in the ITO, reduces the energy consumption of equipment for preparing the bottom electrode again, and reduces the material cost and the preparation cost; under the same preparation condition, the prepared battery device has photoelectric conversion efficiency higher than that of the device under the condition of first use, can realize repeated recycling of the metal oxide type conductive electrode, can maintain the photoelectric conversion efficiency during first use after 7 times of repeated recycling, and has no influence on the stability.
Drawings
FIG. 1: the invention is a schematic diagram of a recycling process;
FIG. 2: based on a PBDB-T-2F and IT-4F photovoltaic system, repeatedly using ITO as a device J-V diagram of a substrate electrode for many times;
FIG. 3: based on a P3HT PCBM photovoltaic system, repeatedly using FTO as a device J-V diagram of a substrate electrode for many times;
FIG. 4: the invention recovers the atomic force microscope picture of the surface of the transparent conductive electrode;
FIG. 5: the invention can be used repeatedly to form the ITO stability curve.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The present invention is described in detail below by way of examples, it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make some insubstantial modifications and adaptations of the present invention based on the above-mentioned disclosure.
Example 1
A method for recycling a transparent conductive electrode of an organic solar cell comprises the following steps:
(1) selecting used ITO/ZnO/PBDB-T-2F, IT-4F/MoO3Placing the/Ag device in chloroform solvent, oscillating at 53KHz for 15min to remove active layer PBDB-T-2F, IT-4F, and upper interface layer MoO3And a metal top electrode Ag.
(2) Then placing the ITO film in a lactic acid solution with the volume concentration of 3%, and oscillating the solution for 15min under the ultrasonic condition of 53KHz to remove ZnO and residual Ag on the surface of the ITO film.
(3) Placing the recovered ITO transparent conductive electrode in deionized water containing a small amount of detergent for ultrasonic cleaning for 15 minutes, and gently kneading the transparent conductive electrode to remove impurities such as grease, dust, dirt, ions and the like on the surface; then placing the mixture in deionized water for ultrasonic cleaning for 15 minutes; then respectively placing the recovered conductive glass electrodes in acetone, absolute ethyl alcohol, chloroform and isopropanol solutions for ultrasonic cleaning for 15 minutes, placing the cleaned electrodes in a drying oven for drying for later use, wherein the drying temperature is 85 ℃, and drying for 20 minutes;
(4) the processed ITO is used as a bottom electrode, and a photovoltaic device with the same specification as the original device is prepared under the same preparation conditions, namely a ZnO layer is prepared on the surface of the photovoltaic device (the precursor solution is zinc acetate, ethylene glycol monomethyl ether, ethanolamine, =1 g, 10ml, 0.28 ml, spin coating, 30 s at 3000 rpm, and thermal annealing treatment at 200 ℃ for 1 h). Then, a PBDB-T-2F: IT-4F active layer (PBDB-T-2F: IT-4F =1:1, both concentrations are 10 mg/ml, solvent is chlorobenzene containing 0.5% of DIO additive, spin coating is carried out at 1500 rpm for 60 s, and thermal annealing treatment is carried out at 120 ℃ for 10 min). Then, 10 nm MoO is evaporated on the surface of the active layer in sequence3And 80 nm of Ag.
After 7 times of recycling tests, the device results are shown in fig. 2, and when the ITO transparent conductive electrode is recycled to the 7 th time, the photoelectric conversion efficiency of the ITO transparent conductive electrode is slightly lower than that of the ITO transparent conductive electrode used for the first time, but the efficiency can still be maintained at 11.62%. In the recycling process, as shown in fig. 5, the photoelectric stability was substantially the same as that in the first use, and the attenuation degree was maintained at a level comparable to that in the first use.
Example 2
A method for recycling a transparent conductive electrode of an organic solar cell comprises the following steps:
(1) selecting a used FTO/PEDOT (PSS/P3 HT) PCBM/LiF/Al device as an object, placing the object in a chlorobenzene solvent under the ultrasonic condition of 53KHz for oscillation for 20min, and fully removing an active layer, LiF and Al on the device;
(2) and placing the mixture in an acetic acid solution with the volume concentration of 5%, and oscillating for 15min under the ultrasonic condition of 53KHz to remove PEDOT, PSS and residual Al on the surface of the FTO.
(3) Placing the recovered FTO transparent conductive electrode in deionized water containing a small amount of detergent for ultrasonic cleaning for 15 minutes, and gently kneading the transparent conductive electrode to remove impurities such as grease, dust, dirt, ions and the like on the surface; then placing the mixture in deionized water for ultrasonic cleaning for 10 minutes; then respectively placing the recovered conductive glass electrodes in acetone, absolute ethyl alcohol, chloroform and isopropanol solutions, ultrasonically cleaning for 10 minutes, placing the cleaned electrodes in a drying oven, and drying for later use at the drying temperature of 90 ℃ for 25 minutes;
(4) taking the FTO treated in the step (3) as a bottom electrode, preparing a photovoltaic device with the same specification as the original by the same preparation regulation, and specifically preparing a PEDOT (PSS) layer on the surface of the FTO (spin coating: 3000 rpm, 30 s, and 120 ℃ thermal annealing treatment for 20 min); then preparing a P3HT PCBM active layer (P3 HT PCBM =1:1, the concentration of the two is 20 mg/ml, the solvent is o-dichlorobenzene, the spin coating is 1100 rpm, the 30 s thermal annealing treatment is carried out at 110 ℃ for 10 min); and then 5 nm LiF and 100 nm Al are evaporated on the surface of the active layer in sequence. The results of the device after 5 iterations of the recycling test are shown in fig. 3.
Example 3
A method for recycling a transparent conductive electrode of an organic solar cell comprises the following steps:
(1) selecting a used ITO/ZnO/CuPc/PCBM/LiF/Al device as an object, placing the object in a chlorobenzene solvent under the 53KHz ultrasonic condition, and oscillating for 20min to fully remove an active layer, LiF and Al on the device;
(2) placing the ITO film in a mixed solution of acetic acid with the volume concentration of 1% and the volume of the acetic acid, oscillating for 15min under the ultrasonic condition of 53KHz, and performing ultrasonic treatment to remove ZnO and residual Al on the surface of the ITO.
(3) Placing the recovered ITO transparent conductive electrode in deionized water containing a small amount of detergent for ultrasonic cleaning for 10 minutes, and gently kneading the transparent conductive electrode to remove impurities such as grease, dust, dirt, ions and the like on the surface; then placing the mixture in deionized water for ultrasonic cleaning for 15 minutes; then respectively placing the recovered conductive glass electrodes in acetone, absolute ethyl alcohol, chloroform and isopropanol solutions in sequence, ultrasonically cleaning for 12 minutes, placing the cleaned electrodes in a drying oven, and drying for later use at the drying temperature of 80 ℃ for 30 minutes;
(4) preparing a photovoltaic device with the same specification as the original by using the FTO treated in the step (3) as a bottom electrode and adjusting the same preparation, and specifically preparing a ZnO layer on the surface of the photovoltaic device (precursor solution is zinc acetate: ethylene glycol monomethyl ether: ethanolamine =1 g: 10ml:0.28 ml, spin coating: 3000 rpm, 30 s, and 200 ℃ thermal annealing treatment for 1 h); then, a CuPc: PCBM active layer (20 mg of CuPc and 20 mg of PCBM are dissolved in 1 ml of mixed solution of dichloromethane and trifluoroacetic acid (1:1), dissolved in dichlorobenzene according to the mass ratio of 75:25, and prepared by a scraper method) is prepared); and then 5 nm LiF and 100 nm Al are evaporated on the surface of the active layer in sequence.
The raw materials of the dilute weak acid with the volume ratio of 1-5 percent are all prepared by analytical purification.
In the preparation process, the alkaline solutions such as ammonia water, sodium hydroxide, sodium carbonate, sodium bicarbonate and the like are selected in the step (2), which can also have an effect on removing the lower interface layer, but the surface structure of the recovered transparent conductive electrode can not be controlled finally, even the surface of the transparent conductive electrode can be damaged, and the anisotropy and the stability of the photoelectric property of the transparent conductive electrode can not be ensured.
Claims (3)
1. Organic solar energyThe method for recycling the transparent conductive electrode of the battery is characterized by comprising the following steps: the method comprises the following steps of putting a waste organic photovoltaic device into an organic solvent to remove a metal top electrode, an upper interface layer and a light activity layer of the device, then putting the device into a dilute weak acid aqueous solution to remove a residual metal top electrode and a residual lower interface layer, so as to obtain a recyclable metal oxide type transparent conductive electrode, and then taking the recycled metal oxide type transparent conductive electrode as a bottom electrode to prepare the organic photovoltaic device; the organic photovoltaic device comprises a solar cell with an active layer made of organic polymer or an organic conjugated micromolecule solar cell, wherein the organic polymer is P3HT PCBM, PBDB-T-2F IT-4F, PTB7 PC71BM or PPV, CdTe, and the conjugated small molecule is CuPc, PCBM or DR3TBDT2T, PC71BM; the transparent conductive electrode comprises an indium tin oxide conductive electrode, a fluorine-doped tin dioxide conductive electrode or an aluminum-doped zinc oxide conductive electrode, and the lower interface layer specifically comprises ZnO and TiO2、SnO2、PEDOT:PSS、MoO3、Ag2O, NiO; the organic solvent is one of chloroform, o-dichlorobenzene, chlorobenzene and carbon disulfide solvent; the weak acid in the dilute weak acid aqueous solution is one or more of lactic acid, acetic acid, propionic acid, boric acid, phytic acid and oxalic acid.
2. The method according to claim 1, wherein the method comprises the following steps: the volume concentration of the dilute weak acid aqueous solution is 1-5%.
3. A method for recycling a transparent conductive electrode of an organic solar cell is characterized by comprising the following steps:
(1) placing the waste organic photovoltaic device in a solvent capable of dissolving the material of the photoactive layer, and fully removing the photoactive layer, an upper interface layer and a metal top electrode thereof under the ultrasonic oscillation condition;
(2) after the step (1), placing the transparent conductive electrode with a part of metal electrode and the lower interface layer left on the surface in a 1-5% diluted acid aqueous solution, and carrying out ultrasonic cleaning until the surface of the transparent conductive electrode is clean, wherein the metal top electrode is Al, Ag or Ca;
(3) placing the recovered metal oxide type transparent conductive electrode in deionized water containing a small amount of detergent for ultrasonic cleaning for 10-15 minutes, and gently rubbing the transparent conductive electrode to remove grease, dust, dirt and ionic impurities on the surface; then placing the mixture in deionized water for ultrasonic cleaning for 10-15 minutes; then respectively placing the recovered transparent conductive electrode in acetone, absolute ethyl alcohol, chloroform and isopropanol solution, ultrasonically cleaning for 10-15 minutes, placing the cleaned electrode in a drying oven, and drying for later use at 80-90 ℃ for 20-30 minutes;
(4) the recovered transparent conductive electrode is taken as a bottom electrode, and a lower interface layer, an optical active layer, an upper interface layer and a metal top electrode are sequentially prepared on the bottom electrode;
(5) and (4) repeating the steps (1) - (4) when the recycling and reusing are carried out again.
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