CN111063805A - Organic-inorganic perovskite solar cell and preparation and recovery method - Google Patents
Organic-inorganic perovskite solar cell and preparation and recovery method Download PDFInfo
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Abstract
An organic-inorganic perovskite solar cell, which comprises an ITO electrode substrate/SnO2Electron transport layer/perovskite material active layer/hole transport layer/nanoporous gold thin film. The nano porous gold film is characterized in that a gold-silver alloy film is kept in nitric acid with the concentration of 69wt% for 6 hours, then the nano porous gold film is washed three times by deionized water, and drying treatment is carried out. The simple transfer technology transfers the porous metal film electrode to the organic-inorganic perovskite solar cell, simplifies the preparation process, reduces the energy consumption and saves the preparation cost. The short-circuit current density of the prepared organic-inorganic perovskite solar cell reaches 21.1mA/cm2High conversion efficiency of 19.0% is obtained, and the stability is good. Reduce the consumption of noble metal materials and the environmental pollution of metals,lays a foundation for realizing the commercial application of the organic-inorganic perovskite solar cell.
Description
Technical Field
The invention belongs to the technical field of perovskite solar cells, and particularly relates to an organic-inorganic perovskite solar cell and a preparation and recycling application method thereof.
Background
In recent years, the energy conversion efficiency of the metal organic-inorganic perovskite solar cell has been increased to 25.2% unprecedentedly and has attracted attention, and the rapid increase of the efficiency of the metal organic-inorganic perovskite solar cell is mainly due to the metal organic-inorganic perovskite material having excellent characteristics, such as a strong light absorption coefficient in the visible light range, a long-range carrier diffusion capability, a low exciton binding energy, a high carrier mobility, and a variable energy band. The metal organic-inorganic perovskite solar cell module mainly comprises a glass substrate/electrode/carrier transmission layer/perovskite material active layer/carrier transmission layer/contact electrode. The contact electrode is made of Au, Cu, Ag and Al metal materials. These metal materials are usually prepared by conventional vacuum evaporation technology, and the large-scale application of noble metals greatly increases the cost of solar cells and limits the industrial application process. Due to the ubiquitous instability, the energy return time of the metal organic-inorganic perovskite solar cell adopting the noble metal electrode is prolonged, and the metal electrode obtained by the traditional technology can only be used once but cannot be recycled, so that the resource waste and the ecological environment damage are aggravated.
Accordingly, many researchers have attempted to develop various alternative materials or more excellent material morphologies to replace the conventional vacuum evaporation technique. The carbon material has low cost, excellent conductivity and high stability, and becomes a more accessible material for the contact electrode of the metal organic-inorganic perovskite solar cell. Thus, various techniques are applied to the preparation of carbon material electrodes, such as a scalpel blade technique, a direct transfer technique, an ink jet technique, an embedding technique, and the like. However, due to the fragile interface contact between the hole transport layer material and the carbon material and the unreasonable energy band matching, the energy conversion efficiency of the metal organic-inorganic perovskite solar cell obtained by the technologies is always lower than that of the traditional evaporated metal electrode cell. In order to improve the interface contact and energy band matching problems, special treatments are used to modify carbon material electrodes, such as p-type semiconductor material doping, metal ion doping, solution exchange techniques. Although the energy conversion efficiency of the metal organic-inorganic perovskite solar cell of the carbon material electrode is improved, the current technology is still too complex, and the energy conversion efficiency is still lower than that of the traditional metal evaporation electrode cell. Furthermore, the carbon material electrode can only be used once and cannot be recycled.
In order to realize the repeated recycling of electrode materials or electrode films, a metal organic-inorganic perovskite solar cell structure with a mesoporous integrated structure is adopted on the mesoporous nickel and nano-pore metal electrodes. However, these solutions cannot always eliminate the complicated preparation process of conventional vacuum evaporation. And the energy conversion efficiency of the metal organic-inorganic perovskite solar cell is greatly reduced after the electrodes are recycled. Because in these structures, the metal organic-inorganic perovskite materials cannot form flat thin films, resulting in different carrier transport distances and carrier recombination losses. Therefore, it is necessary and urgent to develop a simple electrode preparation technology capable of being recycled many times.
Disclosure of Invention
A first object of the present invention is to provide an organic-inorganic perovskite solar cell having a nanoporous metal thin film electrode.
The invention also aims to provide a preparation method of the organic-inorganic perovskite solar cell.
The invention is realized according to the following scheme:
an organic-inorganic perovskite solar cell comprises an ITO electrode substrate, an electron transport layer, a perovskite material active layer, a hole transport layer and a metal thin film electrode from bottom to top in sequence; the method is characterized in that: the metal thin film electrode is a nano porous metal thin film electrode which is attached with the hole transport layer; the nano porous metal film electrode is a nano porous gold film electrode which is composed of mutually connected nano particles, the size of the nano particles is about 18-22nm, and the pore diameter of nano pores on the surface of the nano particles is about 20-30 nm.
We find that the surface of the nano-porous gold film electrode has a porous structure, the surface energy of the film is high, and effective binding force exists when the nano-porous gold film electrode and a hole transport layer are subjected to patch compounding, so that the nano-porous gold film electrode can be tightly and uniformly attached to the hole transport layer.
Further, in order to enhance the bonding force between the porous gold thin film electrode and the hole transport layer more significantly, dry ethanol is used as an adhesive in the attaching process.
Further, the nanoporous gold film electrode is specifically prepared by soaking a gold-silver alloy film in nitric acid (the concentration of the nitric acid is 69 wt%) for 6 hours, then cleaning the film with deionized water, transferring the cleaned nanoporous gold film into a filtering membrane, loading the filtering membrane on the membrane, and drying the membrane.
Further, the hole transport layer and the nano-porous gold film electrode are bonded in a surface mount manner, specifically, the filtration membrane loaded with the nano-porous gold film is lightly attached to the hole transport layer, then dry ethanol is titrated on the back surface of the filtration membrane, redundant dry ethanol solution is removed by spin-drying at 5000 r/min, after spin-coating, the filtration membrane is taken away, and finally the transferred organic-inorganic perovskite solar cell with the ITO electrode substrate, the electron transport layer, the perovskite material active layer, the hole transport layer and the nano-porous gold film electrode is placed in a vacuum box and placed for 12-24 h.
According to the organic-inorganic perovskite solar cell, the hole transport layer is in uniform contact with the nano porous gold film electrode, no gap exists, excellent binding force exists between the porous gold film electrode and the hole transport layer interface, so that the porous gold film electrode and the hole transport layer are tightly combined, the whole structure ensures that the cell has excellent photovoltaic efficiency and stability, the nano porous gold film can be repeatedly utilized for multiple times to prepare the solar cell, and the excellent photovoltaic efficiency and stability of the solar cell are maintained unchanged.
The preparation method of the organic-inorganic perovskite solar cell is characterized by comprising the following steps: the method specifically comprises the steps of ITO substrate pretreatment, electron transport layer preparation, perovskite material active layer preparation, nano porous gold film preparation, hole transport layer preparation and nano porous gold film transfer; the preparation method of the nano porous gold film comprises the steps of soaking the nano gold-silver alloy film in nitric acid, and then cleaning the nano porous gold film by using deionized water to remove chemical substances remained in pores; transferring the cleaned nano porous gold film into a filtering membrane in an aqueous solution, naturally drying, and loading the nano porous gold film on the filtering membrane.
Further, the concentration of the nitric acid is 69wt%, and the soaking time is 6 h.
Further, the transfer of the nano-porous gold film is to directly transfer the prepared nano-porous gold film from the filtration membrane loaded with the nano-porous gold film to the prepared hole transport layer; the method specifically comprises the steps of lightly sticking a filtering filter membrane loaded with a nano-porous gold film on a hole transport layer, titrating dried ethanol, taking away the filtering filter membrane, and finally placing the transferred organic-inorganic perovskite solar cell with an ITO electrode substrate, an electron transport layer, a perovskite material active layer, a hole transport layer and a nano-porous gold film electrode in a vacuum box for 12-24 hours. The contact uniformity and the bonding force between the nano-porous gold film and the hole transport layer are effectively increased in the transfer process.
Further, the step of titrating the dried ethanol is to titrate the dried ethanol on the back of the filter membrane so that the dried ethanol completely covers the surface of the filter membrane, and the redundant dried ethanol is removed by spin-drying at 5000 r/min.
Most particularly, the preparation method of the organic-inorganic perovskite solar cell comprises the following steps:
(1) ITO substrate pretreatment
Spraying zinc oxide powder on the surface of the ITO substrate until the surface of the ITO substrate is completely covered, then washing the ITO substrate by hydrochloric acid with the concentration of 6M, then sequentially cleaning by a detergent with the concentration of 1wt%, and finally performing ultrasonic cleaning by using acetone, isopropanol and deionized water for 10min in each ultrasonic step. Drying the cleaned ITO substrate by using an air gun, and slicing and storing in a drying box;
(2) preparation of electron transport layer
Treating the ITO substrate with ozone for 15min, and then treating the ITO substrate with 5wt% SnO2The nano particle water solution is taken as spin coating liquid to carry out spin coating on the ITO substrate, the spin coating procedure is 3000 revolutions for 30 seconds, and SnO is prepared2Heating the ITO substrate of the electron transmission layer at 150 ℃ for 30min, naturally cooling, and storing in a drying oven;
(3) preparation of perovskite material active layer and passivation layer
a. Dissolving CsI in DMSO to form solution A; then adding PbI2FAI, MABr and PbBr2Sequentially adding the mixed solution into a mixed solvent of DMF and DMSO with the volume ratio of 4:1 to form a solution B, and then uniformly mixing the solution A and the solution B to form a precursor mixed solution; the molar volume ratio of the CsI to the DMSO in the solution A is 1:2mol/L, and the molar volume ratio of the PbI in the solution B is 1:2mol/L2FAI, MABr and PbBr2In a molar ratio of PbI2：FAI：MABr：PbBr21.1: 1: 0.2:0.2 of which PbBr2The molar volume ratio of the precursor solution to the mixed solvent is 1:5mol/L, and the mixed volume ratio of the solution A to the solution B in the precursor mixed solution is 3: 0.14;
b. firstly, spin-coating the precursor mixed solution on an electron transport layer by a spin-coating program of 1000 revolutions and 10 seconds, then continuing spin-coating by a spin-coating program of 6000 revolutions and 20 seconds, quickly splashing toluene on the spin-coated perovskite precursor mixed solution after the spin-coating is finished, then heating to 150 ℃, and preserving heat for 10min to form a perovskite material active layer; preparing and forming a mixed solution according to the proportion relationship of 1mL of chlorobenzene dissolved with 10mg of PMMA and 1.5mg of spiro-OMeTAD, continuing spin coating, wherein the spin coating procedure is 4000 to 30s, and after the spin coating is finished, carrying out spin coating on the SnO with the characteristics of spin coating2Heating ITO substrate of electron transport layer on heating table at 70 deg.C 3Forming a compact passivation layer after 0min, and then naturally cooling;
(4) preparation of hole transport layer
Dissolving spiro-OMeTAD, Li-TFSI, Co (4-tert-butyl pyridine-2-1H-pyrazole) 3.3 TFSI and TBP in chlorobenzene according to a molar ratio of 6:3:0.9:10, wherein the molar volume ratio of TBP to chlorobenzene is 1:10mol/L, spin-coating the prepared mixed solution on the perovskite material active layer, wherein the spin-coating procedure is 4000 to 30s, and completing the spin-coating to obtain the perovskite material with the SnO2The electron transmission layer, the perovskite material active layer and the ITO substrate are placed on a heating table and heated for 30min at 70 ℃; then naturally cooling;
(5) preparation of nano porous gold film
Soaking the gold-silver alloy film in 69wt% nitric acid for 6h, and then cleaning the nano porous metal film by using deionized water to remove chemical substances remaining in pores; transferring the cleaned nano porous gold film into a filtering membrane in an aqueous solution, naturally drying, and storing in a clean box;
(6) nanoporous gold film transfer
Lightly sticking the filtration membrane loaded with the nano porous gold film on the hole transport layer, then titrating a proper amount of dry ethanol on the back surface of the filtration membrane until the back surface of the filtration membrane completely covers the surface of the filtration membrane, increasing the direct contact force of the nano porous gold on the hole transport layer, removing the redundant dry ethanol solution by adopting the way of rotation at 5000 r/min, taking away the filtration membrane after the rotation, and finally placing the obtained organic-inorganic perovskite solar cell with the ITO electrode substrate, the electron transport layer, the perovskite material active layer, the hole transport layer and the nano porous gold film electrode structure in a vacuum box for 12-24h to increase the contact and the binding force between the nano porous gold film and the hole transport layer.
According to the preparation method, a simple patch type transfer metal film electrode is adopted to replace a complex high-energy-consumption vacuum evaporation technology, and the nano porous metal film and the hole transport layer are tightly bonded together, so that the organic-inorganic perovskite solar cell prepared by the electrode keeps excellent photovoltaic efficiency, the porous metal electrode is convenient and simple to recover when being repeatedly used, the integrity of the porous metal film can be well kept, and the performance of the solar cell is not influenced when being repeatedly used.
Further, the recycling application method of the nano porous gold film electrode in the organic-inorganic perovskite solar cell specifically comprises the steps of cleaning the solar cell by using acetone, and collecting the nano porous gold film after cleaning; transferring the nano porous gold film to a new filtering membrane in an acetone solution; cleaning the transferred nano porous gold film for multiple times by using acetone to remove residual chemical substances so as to avoid the reduction of the conductivity of the nano porous gold film; and (4) repeating the steps (1) - (4) and (6) when the nano-porous gold film is recycled after recovery.
The invention has the following beneficial effects:
(1) the invention adopts a simple transfer technology to transfer the porous metal film electrode to the organic-inorganic perovskite solar cell, replaces the traditional complex preparation technology of vacuum evaporation, simplifies the preparation technology, reduces the energy consumption and saves the preparation cost.
(2) The short-circuit current density of the prepared organic-inorganic perovskite solar cell reaches 21.1mA/cm under the condition of not adopting the traditional evaporation2High conversion efficiency of 19.0% is obtained, and the stability is good.
(3) The organic-inorganic perovskite solar cell prepared by the invention has narrow efficiency distribution, and the nano porous gold film electrode on the surface can realize repeated cyclic utilization under the condition of keeping the high efficiency of the cell, thereby further reducing the preparation cost and the energy return time of the organic-inorganic perovskite solar cell, reducing the consumption of noble metal materials and reducing the metal environmental pollution, and laying a foundation for realizing the commercial application of the organic-inorganic perovskite solar cell.
Drawings
FIG. 1: the invention relates to a flow chart for preparing an organic-inorganic perovskite solar cell and recycling a nano porous gold film;
FIG. 2: the invention discloses a schematic diagram of the preparation of an organic-inorganic perovskite solar cell, the transfer process and the recycling process of a nano porous gold film;
FIG. 3: testing the shapes of the surface of the nano porous gold film and the interface of the battery; (a) testing the surface roughness of an atomic force microscope, (b) testing the surface of the nano porous gold film by a scanning electron microscope;
FIG. 4: the invention relates to a sectional view of an organic-inorganic perovskite solar cell device;
FIG. 5: the invention relates to a J-V curve chart of an organic-inorganic perovskite solar cell performance test and a prepared cell example;
FIG. 6: characterizing section characteristics of the evaporated gold film and the nano-porous gold film electrode under secondary recycling; (a) is a gold evaporation plated film, (b) a nano porous gold film;
FIG. 7: the performance representation of the secondary utilization of the evaporated gold film and the nano porous gold film electrode; (a) vapor plating a gold film electrode, (b) a nano porous gold film electrode;
FIG. 8: the photo display of the nano porous gold film electrode in 6 times of cyclic utilization of the solar cell is carried out;
FIG. 9: J-V curve diagram of performance of the nano porous gold film electrode after 12 times of cyclic utilization;
Detailed Description
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 to the present invention based on the above-mentioned disclosure.
Materials used in the present invention:
an ITO electrode substrate with the resistance of 10 omega, 15 wt% SnO with the particle size of 10-15nm2Aqueous nanoparticle solution, lead iodide (PbI)299.99%), lead bromide (PbBr)299.99%), methyl ammonium bromide (MABr,>98.0%), formamidine hydroiodide (FAI,>98.0%), cesium iodide (CsI, 99.9%), polymethyl methacrylate (PMMA, powder particles with a molecular weight of 15000), tert-butylpyridine (TBP), Co (4-tert-butylpyrindiyl-2-1H-pyrazole) 3.3 TFSI, Dimethylformamide (DMF)Dimethyl sulfoxide (DMSO), chlorobenzene, toluene, ethanol, isopropanol, 2,2',7,7' -tetrakis (N, N-bis 4-methoxylamine) -9,9' -spirobifluorene powder (spiro-OMeTAD), lithium bistrifluoromethanesulfonylimide powder (Li-TFSI), acetone, filter membranes, zinc oxide powder, hydrochloric acid, nitric acid, Au35Ag65And (3) an alloy film.
Wherein Co (4-tert-butyl pyridine-2-1H-pyrazole) 3.3 TFSI was purchased from Sigma Aldrich trade company, Inc., Germany.
Au35Ag65The alloy film is prepared by the preparation method disclosed in patent CN 102051497A.
All chemicals and solutions were used directly after purchase without additional purification.
Example 1
A preparation method of an organic-inorganic perovskite solar cell comprises the following steps:
(1) ITO substrate preparation pretreatment
Uniformly spraying zinc oxide powder on the surface of an ITO substrate 1, cleaning with 6M hydrochloric acid, cleaning with 1wt% detergent to remove oil stains, and sequentially performing ultrasonic cleaning with acetone, isopropanol and deionized water, wherein each ultrasonic step is 10 min. The cleaned ITO substrate 1 was dried with an air gun and cut into 25X 25mm pieces2The detergent is a conventional detergent sold in the market;
(2) preparation of the Electron transport layer (I)
Treating the ITO substrate 1 with ozone for 15min, and then treating 15 wt% SnO2Adding deionized water into the nano-particle aqueous solution to prepare an aqueous solution with the concentration of 5wt% as a spin-coating solution ITO substrate 1, performing spin-coating on the ITO substrate 1 by using the spin-coating solution with the spin-coating procedure of 3000 revolutions and 30 seconds, heating the ITO substrate 1 at 150 ℃ for 30min after the spin-coating, and naturally cooling to form SnO2An electron transport layer 2, which will then have said SnO2The ITO substrate 1 of the electron transmission layer 2 is stored in a drying box;
(3) preparation of perovskite Material active layer and passivation layer (II) - (III)
a. Dissolving CsI in DMSO to form an A solution, wherein the molar volume ratio of CsI to DMSO is 1:2 mol/L; then 1.1mmol PbI is added21mmol FAI, 0.2mmol MABr and 0.2mmol PbBr2Sequentially adding into a mixed solvent of DMF and DMSO with a volume ratio of 4:1 to form a solution B, wherein PbBr is contained2The molar volume ratio of the mixed solvent to the mixed solvent is 1:5 mol/L; then uniformly mixing the solution A and the solution B to form a precursor mixed solution, wherein the volume ratio of the solution A to the solution B is 3: 0.14;
b. firstly, spin-coating the precursor mixed solution by a spin-coating procedure of 1000 revolutions and 10 seconds, then continuing spin-coating by a spin-coating procedure of 6000 revolutions and 20 seconds, quickly splashing toluene on the spin-coated perovskite precursor mixed solution to accelerate the crystallization speed, wherein the color of the ITO substrate is quickly changed from transparent to light brown, then heating the ITO substrate to 150 ℃, and preserving the temperature for 10min to form the dark black perovskite active layer 3. PMMA and spiro-OMeTAD were dissolved in chlorobenzene to form a mixed solution, which was spin-coated on the ITO substrate described above, and PMMA and spiro-OMeTAD were dissolved in 1mL of chlorobenzene to be 10mg and 1.5mg, respectively. The spin coating procedure is 4000 revolutions and 30 seconds, after the spin coating, the ITO substrate is placed on a heating table and heated for 30min at 70 ℃ to form a compact passivation layer 4, and then the compact passivation layer is naturally cooled.
(4) Preparation of hole transport layer (V)
Dissolving 0.06mmol of spiro-OMeTAD, 0.03mmol of Li-TFSI, 0.009mmol of Co (4-tert-butyl pyridine-2-1H-pyrazole) 3.3 TFSI and 0.1mmol of TBP in chlorobenzene, wherein the molar volume ratio of the TBP to the chlorobenzene is 1:10mol/L, and spin-coating the prepared mixed solution on the prepared perovskite material active layer by the spin-coating procedure of 4000 to 30 s; after the spin coating is finished, heating the mixture on a heating table at 70 ℃ for 30min to form a compact cavity transmission product 5, and then naturally cooling the product;
(5) preparation of nano porous gold film
Mixing Au35Ag65Keeping the alloy film in nitric acid with the concentration of 69wt% for 6 hours, and then cleaning the nano porous metal film 7 with deionized water three times to remove chemical substances remained in pores; transferring the cleaned nano-porous gold film 7 into a filtered filter membrane 6 in an aqueous solution by using tweezers, drying and storing in a clean box;
(6) nanoporous gold film transfer (VI) - (VIII)
Lightly sticking a filtering filter membrane loaded with a nano porous gold film on a hole transport layer, then titrating 200 mu L of dry ethanol on the back surface of the filtering filter membrane to increase the direct contact force of nano porous gold on the hole transport layer, removing redundant dry ethanol solution by means of spin-coating at 5000 r/min, after the spin-coating, sticking the filtering filter membrane on the whole side by means of a transparent adhesive tape, then slowly taking down the transparent adhesive tape, taking away the filtering filter membrane, and finally transferring the obtained organic-inorganic perovskite solar cell with the ITO electrode substrate, the electron transport layer, the perovskite material active layer, the hole transport layer and the nano porous gold film electrode structure into a vacuum box to be placed for 12 hours.
In the preparation process, ethanol has certain destructiveness on the photosensitive layer, and the PMMA in the photosensitive layer is combined with the hole transport layer to prevent the ethanol from permeating, so that the active layer is further protected from being damaged.
(7) Recycling of porous gold films (IX) - (XII)
After the organic-inorganic perovskite solar cell is used, the perovskite active layer 3, the passivation layer 4 and the hole transport layer 5 are cleaned and removed in acetone 8, and then the porous gold film is transferred to a filter membrane 11 of a glass substrate 10 to obtain a recovered porous gold film 12; the resulting porous gold film 12 is used for subsequent reuse on new solar cells.
In the embodiment of the invention, the nano-porous gold film is successfully transferred to the organic-inorganic perovskite solar cell by adopting a simple transfer technology, and the high conversion efficiency of 19.0% is obtained without the traditional evaporation condition, as shown in figure 5. And the current-voltage positive and negative sweep deviations of the device are almost negligible. Meanwhile, under the condition of stable input, the nano-porous gold film electrode organic-inorganic perovskite solar cell can maintain a stable output. We prepared 50 cells to examine the reproducibility of this protocol and found that the present invention can be easily reproduced with stable cell efficiency.
We examined nanoporous gold filmsSurface properties, interfacial contact properties and electrical properties. The nano porous gold film is composed of interconnected nano particles, and the size of the nano particles is about 20nm, which shows that the nano porous gold film has high specific surface area. As shown in FIG. 1, the specific surface area of the nanoporous gold thin film was 133m2And/g is far higher than that of the gold-evaporated electrode film. The roughness of the surface of the nanoporous gold thin film was 18.5 ± 1.0nm, as shown in fig. 3. This will help to enhance the interfacial contact between the nanoporous gold film and the hole transport layer material, thereby ensuring that the nanoporous gold film has a conductivity comparable to that of the evaporated gold film electrode.
Table 1. electrical properties and specific surface area tests of evaporated gold films and nanoporous gold films.
The vacuum-evaporated gold electrode was also cleaned using the same protocol to remove the organic-inorganic perovskite material, electron and hole transport layers for comparison. As shown in fig. 7(a), when the evaporated gold electrode is used for secondary cycle, the energy conversion efficiency of the battery is greatly reduced, mainly due to the loss of the fill factor and the open-circuit voltage; and the gold electrode causes large-area breakage after transfer, thereby deteriorating recycling performance. In contrast, the secondary utilization effect of the nano-porous gold electrode is much higher than that of the evaporated gold electrode, and as shown in fig. 7(b), the efficiency of the organic-inorganic perovskite solar cell of the nano-porous gold thin film electrode after secondary utilization is basically kept stable.
In the recycling process of the vacuum evaporation gold film electrode, a very large cavity exists between the electrode and the hole transport layer, so that the direct contact between the film electrode and the hole transport layer and the transport of carriers are seriously reduced, as shown in fig. 6 (a). In contrast, the nanoporous gold film prepared by the invention is tightly attached to the hole transport layer film, as shown in fig. 6(b), the situation that the existence of a cavity obstructs the transport of carriers is avoided, and thus, the nanoporous gold film electrode can be recycled for many times under the condition that the high efficiency of the battery can be maintained.
As shown in fig. 8, the nanoporous gold can still retain a large area without being unusable even under up to 6 cycles. Figure 9 summarizes organic-inorganic perovskite solar cell performance up to 12 times recycling of the nanoporous gold electrodes. It can be seen from fig. 9 that the voltage-current curve remains substantially stable even after 12 cycles.
Compared with the traditional evaporation plating instrument which slowly evaporates metal electrodes in vacuum, the technology of directly transferring the nano porous gold film electrode can bring great economic and environmental benefits. With the increase of cycle times, the cost difference between the organic-inorganic perovskite solar cell of the nano porous gold film electrode and the cell prepared by an evaporation instrument is larger and larger. In the using process, the cost of slowly evaporating the metal electrode on the gold electrode material under the vacuum of the traditional evaporation plating instrument is gradually increased along with the increase of the using times, and the directly transferred nano porous gold film electrode can be recycled for multiple times, so that the input cost of the electrode material is greatly reduced.
Claims (9)
1. An organic-inorganic perovskite solar cell comprises an ITO electrode substrate, an electron transport layer, a perovskite material active layer, a hole transport layer and a metal thin film electrode from bottom to top in sequence; the method is characterized in that: the metal thin film electrode is a nano porous metal thin film electrode which is attached with the hole transport layer; the nano porous metal film electrode is a nano porous gold film electrode which is composed of mutually connected nano particles, the size of the nano particles is about 18-22nm, and the pore diameter of nano pores on the surface of the nano particles is about 20-30 nm.
2. An organic-inorganic perovskite solar cell as defined in claim 1, wherein: dry ethanol is also used as an adhesive in the attaching process.
3. An organic-inorganic perovskite solar cell as defined in claim 1 or 2, wherein: the nano-porous gold film electrode is specifically prepared by soaking a gold-silver alloy film in nitric acid, then cleaning the film by using deionized water, transferring the cleaned nano-porous gold film into a filtered filter membrane, and drying.
4. An organic-inorganic perovskite solar cell as defined in any one of claims 1 to 3, wherein: the method comprises the following steps of adhering a hole transmission layer and a nano-porous gold film electrode in a surface mount type manner, specifically adhering a filtering filter membrane and the nano-porous gold film on the hole transmission layer, titrating dry ethanol on the back surface of the filtering filter membrane, removing redundant dry ethanol solution by means of spin-drying at 5000 revolutions per minute, and finally placing the obtained organic-inorganic perovskite solar cell with an ITO electrode substrate, an electron transmission layer, a perovskite material active layer, a hole transmission layer and the nano-porous gold film electrode in a vacuum box for 12-24 hours after spin-coating.
5. The method of manufacturing an organic-inorganic perovskite solar cell as claimed in claim 1, wherein: the method specifically comprises the steps of ITO substrate pretreatment, electron transport layer preparation, perovskite material active layer preparation, nano porous gold film preparation, hole transport layer preparation and nano porous gold film transfer; the preparation method of the nano porous gold film comprises the steps of soaking the nano gold-silver alloy film in nitric acid, and then cleaning the nano porous gold film by using deionized water; and transferring the cleaned nano porous gold film into a filtering membrane in an aqueous solution, naturally drying, and loading the nano porous gold film on the filtering membrane.
6. The method of manufacturing an organic-inorganic perovskite solar cell as claimed in claim 5, wherein: the nano-porous gold film is transferred by directly transferring the prepared nano-porous gold film from a filtering membrane loaded with the nano-porous gold film to a prepared hole transport layer; the method specifically comprises the steps of lightly sticking a filtration membrane loaded with a nano-porous gold film on a hole transport layer, titrating dried ethanol, taking away the filtration membrane, and finally placing the obtained organic-inorganic perovskite solar cell with an ITO electrode substrate, an electron transport layer, a perovskite material active layer, a hole transport layer and a nano-porous gold film electrode in a vacuum box for 12-24 hours.
7. The method of manufacturing an organic-inorganic perovskite solar cell as claimed in claim 6, wherein: the step of titrating the dried ethanol is to titrate a proper amount of dried ethanol on the back of the filter membrane so that the dried ethanol completely covers the surface of the filter membrane, and the redundant dried ethanol is removed by spin-drying at 5000 r/min.
8. A preparation method of an organic-inorganic perovskite solar cell is characterized by comprising the following steps:
(1) ITO substrate pretreatment
Spraying zinc oxide powder on the surface of the ITO substrate until the surface of the ITO substrate is completely covered, then washing the ITO substrate by hydrochloric acid with the concentration of 6M, then sequentially washing by a detergent with the concentration of 1wt%, and finally carrying out ultrasonic cleaning by using acetone, isopropanol and deionized water for 10min in each ultrasonic step, drying the cleaned ITO substrate by using an air gun, slicing and storing in a drying box;
(2) preparation of electron transport layer
Treating the ITO substrate with ozone for 15min, and then treating the ITO substrate with 5wt% SnO2The nano-particle aqueous solution is taken as spin coating liquid to spin-coat on the ITO substrate, the spin coating procedure is 3000, 30s, and the SnO is prepared2Heating the ITO substrate of the electron transmission layer at 150 ℃ for 30min, and then storing the ITO substrate in a drying box;
(3) preparation of perovskite material active layer and passivation layer
a. Dissolving CsI in DMSO to form solution A; then adding PbI2FAI, MABr and PbBr2Sequentially adding the mixed solution into a mixed solvent of DMF and DMSO with the volume ratio of 4:1 to form a solution B, and then uniformly mixing the solution A and the solution B to form a precursor mixed solution; the molar volume ratio of the CsI to the DMSO in the solution A is 1:2mol/L, and the molar volume ratio of the PbI in the solution B is 1:2mol/L2、FAI、MABr and PbBr2In a molar ratio of PbI2：FAI：MABr：PbBr2= 1.1: 1: 0.2:0.2, wherein PbBr2The molar volume ratio of the precursor solution to the mixed solvent is 1:5mol/L, and the mixed volume ratio of the solution A to the solution B in the precursor mixed solution is 3: 0.14;
b. firstly, performing spin coating on the precursor mixed solution on an electron transport layer for 10s by a spin coating program of 1000 revolutions and 10s, then continuing the spin coating by a spin coating program of 6000 revolutions and 20s, quickly splashing toluene on the spin-coated precursor mixed solution when the spin coating is finished, then heating an ITO matrix to 150 ℃, preserving heat for 10min to form a perovskite active layer, preparing and forming a mixed solution according to the proportion relation of dissolving 10mg of PMMA and 1.5mg of spiro-OMeTAD in 1mL of chlorobenzene, continuing the spin coating, wherein the spin coating program is 4000 revolutions and 30s, and after the spin coating is finished, performing spin coating on the SnO with the SnO2Placing the ITO substrate of the electron transmission layer on a heating table, heating at 70 ℃ for 30min to form a passivation layer, and then naturally cooling;
(4) preparation of hole transport layer
Dissolving spiro-OMeTAD, Li-TFSI, Co (4-tert-butyl pyridine-2-1H-pyrazole) 3.3 TFSI and TBP in chlorobenzene according to a molar ratio of 6:3:0.9:10, wherein the molar volume ratio of TBP to chlorobenzene is 1:10mol/L, spin-coating the prepared mixed solution on the perovskite material active layer, wherein the spin-coating procedure is 4000 revolutions and 30 seconds, and completing the spin-coating to obtain the SnO material2Placing the ITO substrate of the electron transmission layer and the perovskite material active layer on a heating table, and heating for 30min at 70 ℃; then naturally cooling;
(5) preparation of nano porous gold film
Soaking the gold-silver alloy film in nitric acid, and then cleaning the nano porous metal film by using deionized water; transferring the cleaned nano porous gold film into a filtering membrane in an aqueous solution, naturally drying, and storing in a clean box;
(6) nanoporous gold film transfer
Lightly sticking the filtration membrane loaded with the nano-porous gold film on the hole transport layer, titrating a proper amount of dry ethanol on the back surface of the filtration membrane until the surface of the filtration membrane is completely covered, removing redundant dry ethanol solution by adopting spin-drying at 5000 r/min, taking away the filtration membrane after spin-drying, and finally placing the obtained organic-inorganic perovskite solar cell with the ITO electrode substrate, the electron transport layer, the perovskite material active layer, the hole transport layer and the nano-porous gold film electrode structure in a vacuum box for 12-24 h.
9. The method for recycling a porous gold thin film electrode in an organic-inorganic perovskite solar cell as claimed in claim 1, wherein: cleaning the solar cell by using acetone, collecting the nano-porous gold film after cleaning, and transferring the nano-porous gold film to a new filtering filter membrane in an acetone solution; and (4) cleaning the transferred nano porous gold film for multiple times by using acetone, and repeating the steps (1) - (4) and (6) when the nano porous gold film is recycled.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113285028A (en) * | 2021-04-22 | 2021-08-20 | 北方民族大学 | Perovskite solar cell manufacturing method |
| CN115140900A (en) * | 2022-07-20 | 2022-10-04 | 青岛尚禹环保设备科技有限公司 | MABR (moving anaerobic biofilm reactor) process rural sewage treatment equipment |
Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1770401A (en) * | 2005-09-30 | 2006-05-10 | 清华大学 | Process for preparing mesoporous metal counter electrode for dye-sensitized solar cell |
| CN101332438A (en) * | 2008-08-04 | 2008-12-31 | 山东大学 | Method for coating noble metal on nano porous gold and prepared catalyst |
| CN102947945A (en) * | 2010-03-26 | 2013-02-27 | 株式会社东芝 | Solar cell |
| US20130059232A1 (en) * | 2011-09-01 | 2013-03-07 | Gwangju Institute Of Science And Technology | Catalytic metal with nanocup or nanoring structure and electrodes using the same |
| CN103451435A (en) * | 2013-09-02 | 2013-12-18 | 浙江触捷光电科技有限公司 | Method for recovering metal silver from waste in silver pulp screen printing process |
| CN103915263A (en) * | 2014-04-15 | 2014-07-09 | 中国科学院福建物质结构研究所 | Method for recovering supercapacitor and electrode material of supercapacitor |
| US20140268490A1 (en) * | 2013-03-12 | 2014-09-18 | National Taiwan University | Super Capacitor And Method For Manufacturing The Same |
| CN104372300A (en) * | 2014-11-03 | 2015-02-25 | 济南大学 | Preparation method of thickness-controllable nano-porous metal thin film |
| CN104600195A (en) * | 2014-12-22 | 2015-05-06 | 国家纳米科学中心 | Perovskite solar battery and preparation method thereof |
| CN106449985A (en) * | 2016-11-02 | 2017-02-22 | 陕西师范大学 | Perovskite battery having graphene barrier layer and preparation method |
| CN107464882A (en) * | 2017-06-26 | 2017-12-12 | 中国科学院广州能源研究所 | A kind of organic inorganic hybridization perovskite solar cell and preparation method thereof |
| CN107681053A (en) * | 2017-08-09 | 2018-02-09 | 吉林化工学院 | A kind of preparation method for being bonded self-enclosure type perovskite battery |
| CN110000375A (en) * | 2019-04-17 | 2019-07-12 | 中国工程物理研究院激光聚变研究中心 | A kind of superelevation porosity porous metal material and preparation method thereof |
-
2019
- 2019-11-11 CN CN201911095313.9A patent/CN111063805B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1770401A (en) * | 2005-09-30 | 2006-05-10 | 清华大学 | Process for preparing mesoporous metal counter electrode for dye-sensitized solar cell |
| CN101332438A (en) * | 2008-08-04 | 2008-12-31 | 山东大学 | Method for coating noble metal on nano porous gold and prepared catalyst |
| CN102947945A (en) * | 2010-03-26 | 2013-02-27 | 株式会社东芝 | Solar cell |
| US20130059232A1 (en) * | 2011-09-01 | 2013-03-07 | Gwangju Institute Of Science And Technology | Catalytic metal with nanocup or nanoring structure and electrodes using the same |
| US20140268490A1 (en) * | 2013-03-12 | 2014-09-18 | National Taiwan University | Super Capacitor And Method For Manufacturing The Same |
| CN103451435A (en) * | 2013-09-02 | 2013-12-18 | 浙江触捷光电科技有限公司 | Method for recovering metal silver from waste in silver pulp screen printing process |
| CN103915263A (en) * | 2014-04-15 | 2014-07-09 | 中国科学院福建物质结构研究所 | Method for recovering supercapacitor and electrode material of supercapacitor |
| CN104372300A (en) * | 2014-11-03 | 2015-02-25 | 济南大学 | Preparation method of thickness-controllable nano-porous metal thin film |
| CN104600195A (en) * | 2014-12-22 | 2015-05-06 | 国家纳米科学中心 | Perovskite solar battery and preparation method thereof |
| CN106449985A (en) * | 2016-11-02 | 2017-02-22 | 陕西师范大学 | Perovskite battery having graphene barrier layer and preparation method |
| CN107464882A (en) * | 2017-06-26 | 2017-12-12 | 中国科学院广州能源研究所 | A kind of organic inorganic hybridization perovskite solar cell and preparation method thereof |
| CN107681053A (en) * | 2017-08-09 | 2018-02-09 | 吉林化工学院 | A kind of preparation method for being bonded self-enclosure type perovskite battery |
| CN110000375A (en) * | 2019-04-17 | 2019-07-12 | 中国工程物理研究院激光聚变研究中心 | A kind of superelevation porosity porous metal material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| KU Z, XIA X, SHEN H, ET AL.: ""Mesoporous nickel counter electrode for printable and reusable perovskite solar cells"", 《NANOSCALE》 * |
| LI M H, YANG Y S, WANG K C, ET AL.: ""Robust and recyclable substrate template with ultrathin nanoporous counter electrode for organic-hole-conductor-free monolithic perovskite solar cells"", 《ACS APPLIED MATERIALS & INTERFACES》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113285028A (en) * | 2021-04-22 | 2021-08-20 | 北方民族大学 | Perovskite solar cell manufacturing method |
| CN115140900A (en) * | 2022-07-20 | 2022-10-04 | 青岛尚禹环保设备科技有限公司 | MABR (moving anaerobic biofilm reactor) process rural sewage treatment equipment |
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