CN110635046A - Preparation method of carbon-based double-layer electrode and perovskite type solar cell - Google Patents

Preparation method of carbon-based double-layer electrode and perovskite type solar cell Download PDF

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CN110635046A
CN110635046A CN201910899038.XA CN201910899038A CN110635046A CN 110635046 A CN110635046 A CN 110635046A CN 201910899038 A CN201910899038 A CN 201910899038A CN 110635046 A CN110635046 A CN 110635046A
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carbon
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肖俊彦
苏杭
程一兵
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Wuhan University of Technology WUT
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Abstract

The invention provides a preparation method of a carbon-based double-layer electrode and a perovskite type solar cell. Which comprises the following steps: step 1, coating conductive carbon slurry on a flexible conductive layer to form a uniform and flat carbon slurry layer; the carbon slurry layer contains a first organic solvent; step 2, soaking the carbon slurry layer into a replacement solvent to remove the first organic solvent in the carbon slurry layer; and 3, drying the carbon slurry layer to obtain the carbon-based double-layer electrode, wherein the replacement solvent is a second organic solvent which is more volatile than the first organic solvent in the conductive carbon slurry. The double-layer film structure is prepared in advance and then is integrally transferred to the cell, so that the process of stripping the carbon conducting layer from the substrate is omitted, the preparation process is simple, and the top electrode for the perovskite type solar cell can be simply and quickly prepared. Has excellent performance when used in perovskite batteries.

Description

Preparation method of carbon-based double-layer electrode and perovskite type solar cell
Technical Field
The invention relates to the technical field of thin-film solar cells, in particular to a preparation method of a carbon-based double-layer electrode and a perovskite type solar cell.
Background
In recent years, perovskite type solar cells based on perovskite type metal halide light absorption materials develop rapidly, the certified photoelectric conversion efficiency of the perovskite type metal halide light absorption materials reaches 24.2 percent at present, and even exceeds the level of commercial technologies such as polycrystalline silicon solar cells, copper indium gallium selenide solar cells, cadmium telluride solar cells and the like, and great attention is paid to the industrial fields of new energy and new materials.
In order to realize the industrialization of such perovskite-type solar cells as early as possible, it is necessary to further improve the stability of the cells and reduce the costs of production processes and raw materials while ensuring the high efficiency of the cells. Therefore, the conductive carbon material which has good conductivity, chemical stability and energy level matching property, is cheap and easy to obtain and has a simple preparation process is considered to be an ideal top electrode material of the perovskite solar cell. However, the application method of the carbon material in the battery device often needs to depend on non-standardized special process technology. At present, some research groups at home and abroad successfully apply the carbon material to the top electrode of the perovskite solar cell by using the conductive carbon slurry, thereby obtaining good effect. Among them, the physical research institute of the chinese academy of sciences prefabricates the conductive carbon slurry into a conductive carbon film with certain autohension, and then prepares the top electrode by using a pressure transfer mode, so as to avoid the damage of the solvent in the conductive carbon slurry to the Perovskite material or the hole transport material in the battery device, thereby realizing the small-area Perovskite battery (Self-additive macro carbon electrodes for Efficient and Stable Perovskite Solar Cells, advanced functional Materials 2018,28,1802985) based on the carbon electrode with the highest efficiency at present.
However, the preparation method of the perovskite battery based on the conductive carbon film has two disadvantages. Firstly, the preparation of the self-adhesive conductive carbon film involves wet film coating, drying, substrate peeling and other processes, the number of steps is more, and the operation process is relatively complex. Secondly, the self-adhesive conductive carbon film has low conductivity, and although the performance of the self-adhesive conductive carbon film is still good in a small-area battery device, when the self-adhesive conductive carbon film is really used in a large-area practical perovskite solar cell, a large voltage drop is generated when a large working current passes through the conductive carbon film, so that the final device performance is greatly influenced.
Disclosure of Invention
The invention aims to provide a preparation method of a carbon-based double-layer electrode aiming at the defects of the prior art, overcomes the defects of the existing preparation method of the carbon counter electrode of the perovskite type solar cell, and has the advantages of good performance, simple process, low cost and strong universality.
Particularly, the invention provides a preparation method of a carbon-based double-layer electrode, which comprises the following steps:
step 1, coating conductive carbon slurry on a flexible conductive layer to form a uniform and flat carbon slurry layer; the carbon slurry layer contains a first organic solvent;
step 2, soaking the carbon slurry layer into a replacement solvent to remove the first organic solvent in the carbon slurry layer;
step 3, drying the carbon slurry layer to obtain a carbon-based double-layer electrode;
wherein the replacement solvent is a second organic solvent that is more volatile than the first organic solvent in the conductive carbon paste.
Optionally, the method further comprises:
and 4, transferring the carbon-based double-layer electrode to a perovskite layer or a hole transport layer of the perovskite solar cell by taking the carbon layer as the inner side and the flexible conductive layer as the outer side to prepare the top electrode.
Optionally, in step 4, transferring the carbon-based double-layer electrode to a perovskite layer or a hole transport layer of the perovskite solar cell by using a pressure transfer method;
optionally, the pressure is 0.1 to 2.0MPa and the time is 5 to 120 seconds.
Optionally, the conductive carbon slurry is prepared by finely grinding graphite powder with the particle size of 1-30 mu m or carbon black with the particle size of 5-500 nm and low-temperature curing thermoplastic resin.
Alternatively, the thermoplastic resin may be one or more of polyvinyl acetate, ethylene-vinyl acetate copolymer, polyacrylate, polyvinyl chloride, polytetrafluoroethylene, polyamide, polymethyl methacrylate, polyurethane, polystyrene, and the like.
Optionally, the coating method is one or more of a drop coating method, a knife coating method, a spray coating method, a spin coating method, a screen printing method, or a pulling method.
Optionally, the flexible conductive layer is one of metal foil, graphite paper and conductive cloth, and the sheet resistance requirement is <1 Ω/□ (sheet resistance). Graphite paper and conductive cloth are preferred. In contrast, the graphite paper has compressibility during pressure transfer, and the compacted double-layer membrane electrode has good contact with other parts of the battery. The conductive cloth material has small bending resilience, thereby ensuring that the obtained double-layer membrane electrode has good contact property in the battery.
Optionally, the displacement solvent is a low boiling point organic solvent, which is one or more of ethanol, methanol, isopropanol, or acetone.
Optionally, the first organic solvent is one or more organic solvents with high boiling points, such as DMSO, DMF, DMAc, NMP, ketones, esters, hydrocarbons, halogenated hydrocarbons, and the like, and capable of dissolving the thermoplastic resin.
Optionally, the carbon layer of the carbon-based double-layer electrode has a thickness of 0.005-0.5 mm. The thickness of the flexible conductive layer is generally 10 to 200 μm.
The invention also provides a perovskite solar cell, which comprises a transparent conductive substrate, an electron transport layer, a perovskite layer or a hole transport layer, and a carbon-based double-layer top electrode formed on the perovskite layer or the hole transport layer; the carbon-based double-layer top electrode is prepared by the carbon-based double-layer electrode preparation method.
The carbon-based double-layer electrode provided by the invention is prepared by uniformly coating the carbon slurry on the flexible conducting layer, and then soaking the flexible conducting layer in a displacement solvent (which can be a low-boiling-point solvent) to perform solvent displacement. And (4) after the replacement is finished and the carbon-based double-layer electrode is dried, the carbon-based double-layer electrode with certain self-adhesion and lower resistance is obtained. And transferring the carbon-based double-layer electrode to a perovskite layer or a hole transport layer of the perovskite type solar cell without the top electrode prepared in advance by using pressure to prepare the top electrode. Among them, the perovskite type solar cell without a counter electrode prepared in advance may be various different types of perovskite type solar cells. For example, TiO is specifically included2And a semiconductor support layer such as ZnO, and Al2O3Mesoscopic superstructure heterojunction perovskite solar cell with equal insulating material support layers and planar type solar cellPlane heterojunction type perovskite solar cells of the sub-transmission layer and the like. The structures of the perovskite solar cells can be provided with or without a hole transport layer. The carbon-based double-layer top electrode is prepared into a double-layer membrane structure in advance and then is integrally transferred to a battery, and the prepared carbon-based double-layer top electrode is good in conductivity and can be used for large-area perovskite solar batteries.
The preparation method of the carbon-based double-layer electrode provided by the invention has the following beneficial effects:
1. the double-layer film structure is prepared in advance and then is integrally transferred to the cell, so that the process of stripping the carbon conducting layer from the substrate is omitted, the preparation process is simple, and the top electrode for the perovskite type solar cell can be simply and quickly prepared.
2. The preparation process of the top electrode is not influenced by the solvent and the temperature.
3. The method is suitable for various perovskite solar cell structures.
4. The carbon-based double-layer electrode provided by the invention can simultaneously realize effective contact and high conductivity with a battery function layer, and ensures the using effect in the perovskite battery.
5. The carbon-based double-layer electrode provided by the invention has better air tightness and can improve the performance stability of the perovskite battery.
Detailed Description
A preparation method of a carbon-based double-layer top electrode comprises the following steps:
1. coating the conductive carbon slurry on the flexible conductive layer to form a uniform and flat double-layer carbon slurry layer; the double-layer carbon slurry layer contains a first organic solvent;
2. soaking the double-layer carbon slurry layer into a replacement solvent to remove the first organic solvent in the carbon slurry layer;
3. drying the double-layer carbon slurry layer to obtain a carbon-based double-layer electrode;
wherein the replacement solvent is a second organic solvent that is more volatile than the first organic solvent in the conductive carbon paste.
Optionally, the method further comprises:
4. and transferring the carbon-based double-layer electrode to a perovskite layer or a hole transport layer of the perovskite solar cell by taking the carbon layer as the inner side and the flexible conductive layer as the outer side to prepare the top electrode.
More specifically, the device structure of the perovskite solar cell comprises a transparent conductive substrate, an electron transport layer, a perovskite absorption layer, a hole transport layer and a flexible porous carbon counter electrode formed on the perovskite layer or the hole transport layer. The chemical general formula of the light absorption layer material in the perovskite solar cell is ABX3Wherein A ions may include but are not limited to CH3NH3 +(MA+)、NH2CH＝NH2 +(FA+)、Cs+One or more of; b is a divalent metal ion and may include, but is not limited to Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cr2+、Pd2+、Cd2+、Ge2+、Sn2+、Pb2+、Eu2+One or more of; x is a halide ion Cl-、Br-、I-Or pseudohalogen ion CN-、NCO-、NCS-、NCSe-One or more of them. In one embodiment, the perovskite light absorbing material may be selected to be MAPbI3。
In step 1, the conductive carbon slurry may be a commercial conductive carbon slurry directly purchased, or a conductive carbon slurry obtained by sufficiently and uniformly mixing conductive carbon powder, thermoplastic resin and a first solvent. And coating the conductive carbon slurry on the flexible conductive layer to form a uniform and flat carbon slurry layer. The conductive carbon slurry is prepared by finely grinding superfine carbon powder and low-temperature curing thermoplastic resin. The thermoplastic resin may be one or more of polyvinyl acetate, ethylene-vinyl acetate copolymer, polyacrylate, polyvinyl chloride, polytetrafluoroethylene, polyamide, polymethyl methacrylate, polyurethane, polystyrene, and the like. The flexible conductive layer is selected from metal foil, graphite paper, conductive cloth, etc. In a specific embodiment, the flexible conductive layer is preferably made of graphite paper or conductive cloth. The coating method forms a carbon slurry layer on the surface of the flexible conductive layer by using a drop coating method, a blade coating method, a spray coating method, a spin coating method, a screen printing method or a pulling method. The low-temperature cured thermoplastic resin in the conductive carbon paste is the first organic solvent contained in the carbon paste layer. The first organic solvent is one or more organic solvents which are relatively difficult to volatilize, such as organic solvents DMSO, DMF, DMAc, NMP, ketones, esters, hydrocarbons, halogenated hydrocarbons and the like, have high boiling points and can dissolve the thermoplastic resin.
In step 2, the flexible conductive layer coated with the carbon paste layer is soaked in a replacement solvent, and the first organic solvent (i.e., the organic solvent which is difficult to volatilize) in the carbon paste layer is removed by a solvent replacement method. The replacement solvent is a low boiling point organic solvent. The low boiling point organic solvent may be one or more of ethanol, methanol, isopropanol, or acetone. In a preferred embodiment, ethanol, a common reagent, is used as the displacement solvent.
In step 3, after the solvent replacement is completed, the flexible conductive layer attached with the carbon film is taken out and dried, so that the carbon-based double-layer electrode with good conductivity is obtained. Wherein the thickness of the carbon layer is 0.005-0.5 mm.
In step 4, the self-adhesion of the carbon layer is utilized by adopting a pressure transfer method, the carbon layer is used as the inner side, the flexible conductive layer is used as the outer side, and the carbon-based double-layer electrode is transferred onto the perovskite layer or the hole transport layer of the perovskite solar cell.
In a specific embodiment, the carbon-based bilayer electrode is transferred onto the perovskite layer or the hole transport layer by means of pressure transfer. Preferably, the pressure is 0.1-2.0MPa, and the time is 5-120 seconds. The carbon-based double-layer electrode is transferred under the conditions of pressure and time, the flexible conducting layer can be guaranteed not to be damaged basically, and the carbon layer in the carbon-based double-layer electrode has better fitting performance with the perovskite layer or the hole transport layer. The temperature of pressure transfer is normal temperature, so that the energy consumption can be reduced, and the preparation cost can be reduced. In the transfer process, when the pressure is too high, the hardness of carbon powder in the electrode is larger than that of the perovskite material and the hole transmission material below, the battery structure can be damaged, and when the pressure is too low or the time is too short, the carbon layer in the carbon-based double-layer electrode can be in poor contact with the perovskite layer or the hole transmission layer, so that the perovskite solar battery with high conversion efficiency cannot be obtained.
The preparation method of the carbon-based double-layer electrode is suitable for various types of perovskite solar cells, and specifically comprises TiO2And ZnO, etc. as the semiconductor support layer, there is Al2O3The perovskite solar cell comprises a mesoscopic superstructure heterojunction type perovskite solar cell with an insulating material support layer and a planar heterojunction type perovskite solar cell with a planar electron transmission layer, wherein in the structures, the perovskite solar cell can be provided with or not provided with a hole transmission layer.
The invention also provides a perovskite solar cell which comprises a transparent conductive substrate, an electron transport layer, a perovskite layer or a hole transport layer, and a carbon-based double-layer top electrode formed on the perovskite layer or the hole transport layer. The carbon-based double-layer top electrode is prepared by the carbon-based double-layer electrode preparation method. In a specific embodiment, the carbon layer in the carbon-based double-layer electrode has a thickness of 0.005 to 0.5 mm. If the carbon layer thickness in the carbon-based bilayer electrode is too great, it may result in too great a series resistance of the battery, reducing the battery fill factor and battery conversion efficiency. If the thickness is too small, the uniformity of the carbon layer in the carbon-based double-layer electrode during film formation is poor. The thickness of the carbon layer in the carbon-based double-layer electrode is controlled within the range, so that the carbon layer can be better attached to a perovskite layer or a hole transport layer, and the performance of the perovskite solar cell is further improved.
The following detailed description is made with reference to certain specific examples.
Example 1
1) Uniformly mixing graphite powder, acetylene black, thermoplastic polyurethane and cyclohexanone according to a certain proportion to obtain the self-made conductive carbon slurry. And then uniformly blade-coating the carbon slurry on an aluminum foil with the thickness of 10 mu m to form a carbon slurry layer, soaking the carbon slurry layer and the substrate into an ethanol solution at normal temperature for 10 minutes, and replacing and removing the organic solvent which is difficult to volatilize in the carbon film. After the substrate is taken out, ethanol remained in the carbon layer is quickly volatilized in the air, and the carbon-based double-layer electrode with the total thickness of 80 mu m is obtained.
2) The perovskite battery without the hole transport layer is prepared by firstly spin-coating a TiO layer on FTO conductive glass2And (3) annealing the precursor film at 500 ℃ for 1 hour to obtain a dense layer with the thickness of about 20 nm. Then the TiO layer is added into the dense layer2Coating a layer of TiO on the surface of the substrate by spin coating2The slurry was annealed at 500 ℃ for 1 hour to obtain a porous scaffold layer having a thickness of about 150 nm. Followed by a one-step antisolvent process on TiO2And preparing a perovskite absorption layer on the porous support layer. Firstly, dripping prepared perovskite precursor on a bracket layer, soaking for 30s, then, carrying out low-speed spin coating at 1000rpm for 10s, then carrying out high-speed spin coating at 5000rpm for 30s, and quickly dripping 120 mu L chlorobenzene when the high-speed spin coating reaches 15s to obtain a preliminarily crystallized perovskite thin film. Heating at 150 deg.C for 10 min under inert atmosphere, and heating at 100 deg.C for 40 min under vacuum state to obtain methylamine lead iodide MAPbI with good crystallization quality3A perovskite absorption layer.
3) And (3) adhering the flexible porous conductive carbon film to the surface of the perovskite light absorption layer, and pressing for 30 seconds under the conditions of normal temperature and 0.6MPa to obtain the complete perovskite solar cell.
Example 2
1) And uniformly coating the commercial carbon slurry on graphite paper with the thickness of 50 mu m to form a carbon slurry layer, soaking the carbon slurry layer and the substrate into a methanol solution at normal temperature, and replacing and removing the organic solvent which is difficult to volatilize in the carbon film. After the substrate is taken out, the residual methanol in the carbon layer is quickly volatilized in the air, and the carbon-based double-layer electrode with the total thickness of 150 mu m is obtained.
2) Preparing perovskite battery with hole transmission layer, firstly spin coating a layer of TiO on FTO conductive glass2And (3) retreating the precursor film at 500 ℃ for 1 hour to obtain a compact layer with the thickness of about 20 nm. Then adopting a one-step anti-solvent method to react on TiO2And preparing a perovskite absorption layer on the dense layer. Firstly, dripping prepared perovskite precursor on a bracket layer, soaking for 30s, then, carrying out low-speed spin coating at 1000rpm for 10s, then carrying out high-speed spin coating at 5000rpm for 30s, and quickly dripping 120 mu L chlorobenzene when the high-speed spin coating reaches 15s to obtain a preliminarily crystallized perovskite thin film. Heating at 150 deg.C for 10 min under inert atmosphere, and vacuum 1Heating at 00 ℃ for 40 minutes to obtain methylamine formamidine mixed perovskite FA with good crystallization quality0.85MA0.15Pb(I0.95Br0.05)3An absorption layer. And finally, a Spiro-OMeTAD hole transport layer is spin-coated on the perovskite absorption layer.
3) Attaching the carbon-based double-layer electrode prepared in the step 1) to the surface of the hole transport layer, and pressing for 120 seconds under the conditions of normal temperature and 0.1MPa to obtain the complete perovskite solar cell.
Example 3
1) And uniformly coating commercial carbon slurry on conductive cloth with the thickness of 30 mu m to form a carbon slurry layer, and soaking the carbon slurry layer and the substrate into isopropanol solution at normal temperature to replace and remove the organic solvent which is difficult to volatilize in the carbon film. After the substrate is taken out, the isopropanol remained in the carbon layer is quickly volatilized in the air, and the carbon-based double-layer electrode with the total thickness of 230 mu m is obtained.
2) Preparing a perovskite cell with a hole transmission layer by spin-coating a layer of SnO on FTO conductive glass2And (3) annealing the nano-particle dispersion liquid at 180 ℃ for 30 minutes to obtain a compact layer with the thickness of about 20 nm. Then adopting a part of anti-solvent method to prepare SnO2And preparing a perovskite absorption layer on the dense layer. Firstly, dripping prepared perovskite precursor on a bracket layer, soaking for 30s, then, carrying out low-speed spin coating at 1000rpm for 10s, then carrying out high-speed spin coating at 5000rpm for 30s, and quickly dripping 120 mu L chlorobenzene when the high-speed spin coating reaches 15s to obtain a preliminarily crystallized perovskite thin film. Heating at 150 deg.C for 10 min under inert atmosphere, and heating at 100 deg.C for 40 min under vacuum state to obtain cesium formamidine mixed perovskite Cs with good crystal quality0.15FA0.85PbI3An absorption layer. And finally, a Spiro-OMeTAD hole transport layer is spin-coated on the perovskite absorption layer.
3) Attaching the carbon-based double-layer electrode prepared in the step 1) to the surface of the hole transport layer, and pressing for 5 seconds under the conditions of normal temperature and 2MPa to obtain the complete perovskite solar cell.
Comparative example 1
1) Step 1) is the same as step 2) of example 1
2) And (2) evaporating a gold top electrode with the thickness of about 80nm on the perovskite layer in the step 1) to obtain the complete perovskite solar cell.
Comparative example 2
1) Step 1) is the same as step 2) of example 2
2) And (2) evaporating a gold top electrode with the thickness of about 80nm on the perovskite layer in the step 1) to obtain the complete perovskite solar cell.
Comparative example 3
1) Step 1) is the same as step 2) of example 3
2) And (2) evaporating a gold top electrode with the thickness of about 80nm on the perovskite layer in the step 1) to obtain the complete perovskite solar cell.
Comparative example 4
1) Graphite powder, acetylene black, thermoplastic polyurethane and cyclohexanone are uniformly mixed according to a certain proportion to obtain the self-made conductive carbon slurry, refer to example 1. And then uniformly coating the carbon slurry on a polytetrafluoroethylene film to form a carbon slurry layer, soaking the carbon slurry layer and the substrate into an ethanol solution at normal temperature for 10 minutes, and removing the organic solvent which is difficult to volatilize in the carbon film by replacement. After the substrate was taken out, ethanol remaining in the carbon layer was rapidly volatilized in the air, and the carbon film electrode was peeled off from the polytetrafluoroethylene substrate to obtain a carbon film electrode having a total thickness of 80 μm.
2) Step 2) is the same as step 2) of example 1.
3) Attaching the carbon film electrode prepared in the step 1) to the surface of the perovskite layer, and pressing for 30 seconds under the conditions of normal temperature and 0.6MPa to obtain the complete perovskite solar cell.
Comparative example 5
1) And uniformly coating the commercial carbon slurry on a polytetrafluoroethylene film to form a carbon slurry layer, soaking the carbon slurry layer and the substrate into an ethanol solution at normal temperature for 10 minutes, and removing the organic solvent which is difficult to volatilize in the carbon film by replacement. After the substrate is taken out, ethanol remained in the carbon layer is quickly volatilized in the air, and the carbon film electrode with the total thickness of 150 mu m is obtained by peeling the ethanol from the polytetrafluoroethylene substrate.
2) Step 2) is the same as step 2) of example 2.
3) Attaching the carbon film electrode prepared in the step 1) to the surface of the hole transport layer, and pressing for 120 seconds under the conditions of normal temperature and 0.1MPa to obtain the complete perovskite solar cell.
Comparative example 6
1) And uniformly coating the commercial carbon slurry on a polytetrafluoroethylene film to form a carbon slurry layer, soaking the carbon slurry layer and the substrate into an ethanol solution at normal temperature for 10 minutes, and removing the organic solvent which is difficult to volatilize in the carbon film by replacement. After the substrate was taken out, ethanol remaining in the carbon layer was rapidly volatilized in the air, and the carbon film electrode was peeled off from the polytetrafluoroethylene substrate to obtain a carbon film electrode having a total thickness of 230 μm.
2) Step 2) is the same as step 2) of example 3.
3) Attaching the carbon film electrode prepared in the step 1) to the surface of the hole transport layer, and pressing for 5 seconds under the conditions of normal temperature and 2MPa to obtain the complete perovskite solar cell.
The perovskite solar cells prepared in examples 1 to 3 and comparative examples 1 to 6 were tested for performance with a potentiostat under a standard solar simulator, wherein the short circuit current density, open circuit voltage, fill factor, conversion efficiency, i.e. specific data characterizing the stability, are shown in table 1.
TABLE 1 Performance test data (effective area 0.1 cm) for perovskite solar cells2And 1cm2)
Figure BDA0002211199180000061
As can be seen from table 1, the perovskite solar cell of the carbon-based double-layer electrode of the present invention obtains photoelectric conversion efficiency comparable to that of the standard gold electrode cell and better stability when used in both small-area and large-area perovskite solar cells. The main materials in the solar cell belong to semiconductors, the transverse conductivity is poor, and in practical application, a high-conductivity electrode is required to be used as a current collector so as to effectively lead the generated photocurrent out to an external circuit. In the small-area perovskite solar cell, the total current generated by the cell is small, and when the current is transmitted from one end of the carbon film electrode to the other end of the carbon film electrode to enter an external circuit, the distance between the carbon film electrodes is short, so that the Joule loss is small, and the high cell efficiency can be maintained. When the perovskite solar cell is used in a large-area perovskite cell, the total current of the cell is large, the carbon film electrode needed to pass through is far away in the process of being led out to an external circuit, and the resistance is large, so that the joule loss is large. Compared with a single-layer carbon film electrode, the carbon-based double-layer electrode provided by the invention can simultaneously realize effective contact with a battery function layer and high conductivity, wherein the high-conductivity flexible conductive layer can play a role of a current collector, so that the current is prevented from being transmitted in a high-resistance carbon film layer in a long distance, and the carbon-based double-layer electrode has excellent performance when used for a large-area perovskite solar battery and is obviously superior to the performance of the single-layer carbon film electrode. Meanwhile, the preparation process is simple, the cost is low, and the commercialization requirement is met. In addition, the carbon counter electrode has good flexibility, and is suitable for the preparation of flexible solar cells and the roll-to-roll large-area preparation.
Thus, it should be appreciated by those skilled in the art that while a number of exemplary embodiments of the invention have been illustrated and described in detail herein, many other variations or modifications consistent with the principles of the invention may be directly determined or derived from the disclosure of the present invention without departing from the spirit and scope of the invention. Accordingly, the scope of the invention should be understood and interpreted to cover all such other variations or modifications.

Claims (10)

1. A preparation method of a carbon-based double-layer electrode is characterized by comprising the following steps: the method comprises the following steps:
step 1, coating conductive carbon slurry on a flexible conductive layer to form a uniform and flat carbon slurry layer; the carbon slurry layer contains a first organic solvent;
step 2, soaking the carbon slurry layer into a replacement solvent to remove the first organic solvent in the carbon slurry layer;
step 3, drying the carbon slurry layer to obtain a carbon-based double-layer electrode;
wherein the replacement solvent is a second organic solvent that is more volatile than the first organic solvent in the conductive carbon paste.
2. The method of preparing a carbon-based bilayer electrode according to claim 1, wherein: and 4, transferring the carbon-based double-layer electrode to a perovskite layer or a hole transport layer of the perovskite solar cell by taking the carbon layer as the inner side and the flexible conductive layer as the outer side to prepare a top electrode.
3. The method of preparing a carbon-based bilayer electrode according to claim 2, wherein: in step 4, transferring the carbon-based double-layer electrode to a perovskite layer or a hole transport layer of the perovskite solar cell by adopting a pressure transfer method.
4. The method of preparing a carbon-based bilayer electrode according to claim 3, wherein: the pressure is 0.1-2.0MPa, and the time is 5-120 seconds.
5. The method of preparing a carbon-based bilayer electrode according to claim 1, wherein: the conductive carbon slurry is prepared by finely grinding graphite powder with the particle size of 1-30 mu m, carbon black with the particle size of 5-500 nm and low-temperature curing thermoplastic resin; the thermoplastic resin may be one or more of polyvinyl acetate, ethylene-vinyl acetate copolymer, polyacrylate, polyvinyl chloride, polytetrafluoroethylene, polyamide, polymethyl methacrylate, polyurethane, polystyrene, and the like.
6. The method of preparing a carbon-based bilayer electrode according to claim 1, wherein: the coating method is one or more of a dripping coating method, a blade coating method, a spraying method, a spin coating method, a screen printing method or a pulling method.
The replacement solvent is a low-boiling-point organic solvent, and the low-boiling-point organic solvent is one or more of ethanol, methanol, isopropanol or acetone; the first organic solvent is one or more organic solvents which have higher boiling points and can dissolve the thermoplastic resin, such as DMSO, DMF, DMAc, NMP, ketones, esters, hydrocarbons, halogenated hydrocarbons and the like.
7. The method of preparing a carbon-based bilayer electrode according to claim 1, wherein: the flexible conducting layer is one of metal foil, graphite paper and conducting cloth, and the sheet resistance requirement is less than 1 omega/□.
8. The method of preparing a carbon-based bilayer electrode according to claim 1, wherein: the flexible conducting layer is made of graphite paper and conducting cloth.
9. The method of preparing a carbon-based bilayer electrode according to claim 1, wherein: the thickness of the flexible conducting layer is generally 10-200 mu m, and the thickness of the carbon layer of the carbon-based double-layer electrode is 0.005-0.5 mm.
10. A perovskite solar cell comprising a transparent conductive substrate, an electron transport layer, a perovskite layer or a hole transport layer, and a carbon-based bilayer top electrode formed on the perovskite layer or the hole transport layer; the carbon-based double-layer top electrode is prepared by the preparation method of the carbon-based double-layer electrode as claimed in any one of claims 1 to 9.
CN201910899038.XA 2019-09-23 2019-09-23 Preparation method of carbon-based double-layer electrode and perovskite type solar cell Pending CN110635046A (en)

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