CN109802042B - Semitransparent perovskite solar cell electrode and preparation method thereof - Google Patents
Semitransparent perovskite solar cell electrode and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a semitransparent perovskite solar cell electrode and a preparation method thereof, wherein the semitransparent perovskite solar cell electrode is prepared by the following steps: 1) preparing a reduced graphene oxide solution; 2) preparing a nano silver wire dispersion liquid; 3) placing the FTO glass covered with the electron transport layer on a heating table, preparing a perovskite absorption layer on the surface, spin-coating spiro as a hole transport layer, coating the nano silver wire dispersion liquid on the hole transport layer, drying to form a nano silver wire electrode, covering a reduced graphene oxide solution between the spiro and the silver wire, or on the silver wire, or preparing reduced graphene oxide layers on the upper and lower sides of the silver wire, and obtaining the semitransparent perovskite solar cell electrode. The reduced graphene oxide can be bonded with silver wire grid junctions, the resistance of the silver nanowire is reduced, and the transmission performance of electrons is improved, so that the conductivity of the silver wire is enhanced, the series resistance of a battery device is reduced, and the integral photoelectric performance is improved.
Description
Technical Field
The invention belongs to the field of solar cells, and particularly relates to a semitransparent perovskite solar cell electrode and a preparation method thereof.
Background
With the increasing severity of energy crisis and environmental pollution, the development of new clean energy sources is very important. Solar energy is a novel clean energy technology with the greatest prospect due to the advantages of environmental protection, high efficiency, inexhaustibility and the like. In recent years, the perovskite solar cell is rapidly developed due to high efficiency, low cost and large-area production, and the semitransparent cell can be prepared, the photoelectric conversion efficiency of the perovskite solar cell is rapidly improved from 3.8% in 2009 to 23.3% at present, and the perovskite solar cell has wide application prospect. The perovskite solar cell has the great advantage that the preparation of the semitransparent device can be realized by reducing the thickness of the active layer and using the transparent top electrode, so that the perovskite solar cell has great application prospect in the aspects of building integration such as roofs, energy windows, greenhouse applications and the like. In addition, the wearable electronic device has wider application in the future wearable electronic field. The photoelectric conversion efficiency of a semi-transparent cell is partly lost compared to an opaque cell, on the one hand due to the thinner active layer, the absorption of light is reduced, and on the other hand the reflection of light by the transparent top electrode is reduced. Semi-transparent cells, however, have higher power generation efficiency because they have the ability to receive photons from both poles (positive and negative). Furthermore, the semi-transparent perovskite solar cell is easy to realize to form a tandem solar cell with other cells, thereby obtaining a higher efficiency than a single junction silicon solar cell.
The transparent conductive electrode is widely applied to photovoltaic devices, touch screens, liquid crystal displays (L CDs), organic light emitting diodes (O L EDs) and the like due to high transparency and good conductivity, Indium Tin Oxide (ITO) is the most widely applied electrode material in the photoelectric devices at present, but a substitute is urgently needed to be found due to the factors of high price, indium resource shortage, brittleness and the like.
The nano silver wire has high conductivity and light transmissionGood flexibility, low-temperature solution preparation and the like. In order to improve the conductivity and stability of the silver wires, the Choy project group utilizes a chemical growth silver welding method to promote the connection at the intersections of the silver wires, and the conductivity and stability of the silver wires are obviously improved. In 2015, the Brabec task group reports that a silver wire manufactured by a spraying method is used as a top electrode of an inverted perovskite solar cell to obtain a device with an ITO/PEDOT: PSS/MAPbI structure3/PC61BM/Zn O/AgNWs. Wherein at PC61A layer of ZnO is introduced between BM and AgNWs, and the function of ZnO is to adjust work function and ensure PC61Ohmic contact between BM and AgNWs while protecting the perovskite active layer from being damaged by silver wires. The photoelectric conversion efficiency of the final device reaches 8.5%, and the average transmittance reaches 28.4%. In 2017, the marchand group used a silver wire prepared by ink-jet printing for the top electrode of a semitransparent perovskite solar cell, and the device structure of the silver wire was ITO/PEDOT: PSS/MAPbI3-xClx/PC61BM/PEI/AgNWs. The introduction of PEI has the same effect as that of ZnO, namely the work function is adjusted, and meanwhile, the perovskite active layer is protected from being damaged by the silver wire. A translucent perovskite cell device with a device efficiency of 14.17% and an average transmittance of 21.2% was finally obtained.
The graphene has good electrical and optical properties, mechanical properties, heat conduction properties, extremely high charge carrier mobility, and excellent mechanical strength and flexibility. These properties of graphene have led to a great deal of attention and have rapidly become the focus of research. In 2015, the Feng Yan group prepared graphene transparent electrodes on copper mesh using Chemical Vapor Deposition (CVD) and transferred to the device structure of FTO/compact TiO by lamination2/mp-TiO2/MAPbI3-xClxPSS/Graphene, wherein the PEDOT and PSS are used as a modification layer to improve the conductivity of the Graphene by adjusting the Fermi level of the Graphene. Although the conductivity of the graphene is not enough to obtain a high-performance semitransparent perovskite solar cell, the performance of the device can be improved by adjusting the number of layers of the graphene, and the test result shows that when the graphene is two layers, the device has high performanceThe performance is optimal. They further adjusted the thickness of the perovskite active layer and tested the transmittance versus device performance. The results show that the transmittance of the device decreases with increasing film thickness, while the performance increases further. The transmittance of the optimized device at 700nm is between 35 and 20 percent, and the photoelectric conversion efficiency is between 10 and 12 percent.
The nano silver wire is considered to be an ideal choice for replacing an ITO transparent conductive electrode due to the advantages of high conductivity and light transmittance, good flexibility, capability of being prepared by a low-temperature solution method and the like. However, the silver wire obtained by spraying cannot sufficiently exhibit its conductivity due to poor contact between the silver wires, and the silver wire is easily oxidized.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art, and provides a semitransparent perovskite solar cell electrode and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
provided is a semi-transparent perovskite solar cell electrode which is prepared by the following method:
1) preparing a reduced graphene oxide solution: dissolving graphene oxide powder prepared by a Hummers method in pure water to obtain a graphene oxide aqueous solution, adding a reducing agent for reduction, filtering and washing for 2-5 times, dissolving in isopropanol, and performing ultrasonic dispersion to obtain a reduced graphene oxide solution;
2) preparing a nano silver wire dispersion liquid: heating ethylene glycol in an oil bath at 150-180 ℃, adding AgNO into the ethylene glycol after heating for 40-80 min3Continuously adding a PVP solution through a constant flow pump, wherein the adding speed is 2-5 m L/min, continuously reacting for 8-20 min after the addition is finished, separating and purifying after the reaction is finished to obtain a nano silver wire, and dispersing the nano silver wire in isopropanol to obtain a nano silver wire dispersion liquid;
3) preparing a semitransparent perovskite solar cell electrode: placing the FTO glass covered with the electron transport layer on a heating table at the temperature of 80-120 ℃, preparing a uniform and flat perovskite absorption layer on the surface, coating the reduced graphene oxide solution prepared in the step 1) on the perovskite absorption layer according to requirements, drying in vacuum to obtain a reduced graphene oxide layer, then spin-coating spiro as a hole transport layer, then coating the nano silver wire dispersion liquid obtained in the step 2) on the hole transport layer, drying to form a nano silver wire electrode, covering the reduced graphene oxide solution obtained in the step 1) between spiro and a silver wire on a hot bench, or preparing a reduced graphene oxide layer on the silver wire, or preparing the reduced graphene oxide layers on the upper and lower sides of the silver wire to form a 'sandwich' electrode structure of reduced graphene oxide-silver wire-reduced graphene oxide, so as to obtain the semi-transparent perovskite solar cell electrode.
According to the scheme, the reducing agent in the step 1) is one of hydrazine hydrate, sodium borohydride and sodium dodecyl benzene sulfonate.
According to the scheme, the concentration of the graphene oxide aqueous solution in the step 1) is 0.3-0.6 g/L.
According to the scheme, the ultrasonic dispersion conditions in the step 1) are as follows: the temperature is 25-60 ℃, the ultrasonic frequency is 500-20000 Hz, and the ultrasonic dispersion time is 5-8 h.
According to the scheme, the concentration of the reduced graphene oxide solution in the step 1) is 0.2-0.5 g/L.
According to the scheme, the AgNO in the step 2)3The solution is AgNO3The concentration of the ethylene glycol solution is 0.15-0.3 mol/L.
According to the scheme, the AgNO in the step 2)3The volume ratio of the solution to the ethylene glycol is 1: 1 to 6.
According to the scheme, the PVP solution in the step 2) is an ethylene glycol solution of PVP, and the concentration is 0.3-0.6 mol/L.
According to the scheme, the AgNO in the step 2)3AgNO in solution3The molar ratio of the PVP to the PVP in the PVP solution is 1: 1.5 to 2.5.
According to the scheme, the concentration of the nano silver wire dispersion liquid in the step 2) is 2-5 mg/m L.
According to the scheme, the perovskite precursor solution in the step 3) is MAPbI3A perovskite solution.
According to the scheme, the thickness of the perovskite absorption layer in the step 3) is 600-900 nm.
According to the scheme, the thickness of the hole transport layer in the step 3) is 100-500 nm.
According to the scheme, the rotating speed of the spin coating in the step 3) is 1000-5000 r/min, the acceleration is 1000r/min, and the spin coating time is 30 s.
According to the scheme, the thickness of the nano silver electrode in the step 3) is 20-50 nm.
According to the scheme, the thickness of the reduced graphene oxide layer in the step 3) is less than or equal to 2 nm.
The invention also provides a preparation method of the semitransparent perovskite solar cell electrode, which comprises the following steps:
1) preparing a reduced graphene oxide solution: dissolving graphene oxide powder prepared by a Hummers method in pure water to obtain a graphene oxide aqueous solution, adding a reducing agent for reduction, filtering and washing for 2-5 times, dissolving in isopropanol, and performing ultrasonic dispersion to obtain a reduced graphene oxide solution;
2) preparing a nano silver wire dispersion liquid: heating ethylene glycol in an oil bath at 150-180 ℃, adding AgNO into the ethylene glycol after heating for 40-80 min3Continuously adding a PVP solution through a constant flow pump, wherein the adding speed is 2-5 m L/min, continuously reacting for 8-20 min after the addition is finished, separating and purifying after the reaction is finished to obtain a nano silver wire, and dispersing the nano silver wire in isopropanol to obtain a nano silver wire dispersion liquid;
3) preparing a semitransparent perovskite solar cell electrode: placing the FTO glass covered with the electron transport layer on a heating table at the temperature of 80-120 ℃, preparing a uniform and flat perovskite absorption layer on the surface, coating the reduced graphene oxide solution prepared in the step 1) on the perovskite absorption layer according to requirements, drying in vacuum to obtain a reduced graphene oxide layer, then spin-coating spiro as a hole transport layer, then coating the nano silver wire dispersion liquid obtained in the step 2) on the hole transport layer, drying to form a nano silver wire electrode, covering the reduced graphene oxide solution obtained in the step 1) between spiro and a silver wire on a hot bench, or preparing a reduced graphene oxide layer on the silver wire, or preparing the reduced graphene oxide layers on the upper and lower sides of the silver wire to form a 'sandwich' electrode structure of reduced graphene oxide-silver wire-reduced graphene oxide, so as to obtain the semi-transparent perovskite solar cell electrode.
The invention also comprises a semitransparent perovskite solar cell prepared according to the semitransparent perovskite solar cell electrode.
The invention has the beneficial effects that: 1. in the semitransparent perovskite solar cell electrode provided by the invention, the reduced graphene oxide with smaller sheet diameter can be bonded with silver wire grid cross points, the resistance of a silver nanowire is reduced, and the transmission performance of electrons is improved, so that the conductivity of the silver wire is enhanced, the series resistance of a cell device is reduced, and the integral photoelectric performance is improved. 2. Compared with the prior art, the invention realizes the full-solution preparation of the semitransparent perovskite battery, has low cost and is suitable for popularization.
Drawings
FIG. 1 is a graph of efficiency & transmittance of battery devices prepared by spin coating at different spin speeds in example 1 of the present invention;
FIG. 2 is a graph of external quantum efficiency of a battery device prepared by spin-coating a spiro under different rotation speed conditions in example 1;
fig. 3 is a graph of the efficiency of cell devices prepared from Graphene Oxide (GO) and reduced graphene oxide (rGO) of example 2;
fig. 4 is a graph of external quantum efficiency for battery devices prepared from Graphene Oxide (GO) and reduced graphene oxide (rGO) of example 2;
FIG. 5 is a graph of the transmittance of battery electrodes of different thicknesses prepared by different spray amounts in example 3;
FIG. 6 is a graph of the average transmission and sheet resistance of battery electrodes of different thicknesses prepared at different spray levels for example 3;
FIG. 7 is a J-V plot of the pure silver nanowires of example 4, graphene reduction oxide overlaid between the spiro and silver wires, graphene reduction oxide overlaid on the silver wires, and forming a "sandwich" electrode structure of graphene reduction oxide-silver wire-graphene reduction oxide;
FIG. 8 is a graph of the external quantum efficiency of the pure silver nanowires of example 4, reduced graphene oxide overlaid between the spiro and silver wires, reduced graphene oxide overlaid on the silver wires, and a "sandwich" electrode structure formed of reduced graphene oxide-silver wire-reduced graphene oxide;
fig. 9 is a battery stability test chart of the pure silver nanowires, the graphene reduction oxide covered between the spiro and the silver wires, the graphene reduction oxide covered on the silver wires, and the "sandwich" electrode structure formed by the graphene reduction oxide-silver wire-graphene reduction oxide in example 4.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention is further described in detail below with reference to the accompanying drawings.
Example 1
The embodiment provides a preparation method of a semitransparent perovskite solar cell electrode, which comprises the following steps:
preparation of reduced graphene oxide solution
Dissolving graphene oxide powder prepared by a Hummers method in pure water to obtain a graphene oxide aqueous solution with the concentration of 0.3 g/L, adding hydrazine hydrate for reduction, filtering and washing for 3 times, dissolving in isopropanol, and performing ultrasonic dispersion (the ultrasonic dispersion temperature is 25 ℃, the frequency is 500Hz, and the flow rate is 2.5 m)3The ultrasonic dispersion time is 8 hours), and reduced graphene oxide solution with the concentration of 0.2 g/L is obtained;
preparation of nano silver wire dispersion liquid
Heating 80m L ethylene glycol in oil bath pan to 150 deg.C, maintaining the temperature for 80min, and adding AgNO3Is (2) is (50m L, the concentration is 0.15 mol/L), and then passes through a constant flow pumpContinuously adding 50m L PVP ethylene glycol solution (0.3 mol/L), wherein the adding speed is 3m L/min, continuously reacting for 10min after the adding is finished, purifying the solution by using a centrifugal machine through ethanol to obtain a nano silver wire after the reaction is finished, and dispersing the nano silver wire into isopropanol to obtain nano silver wire dispersion liquid with the concentration of 2mg/m L;
third, battery interface treatment
Vacuum evaporation of filtered perovskite precursor solution (0.65 mol/L MAPbI) on FTO glass surface covered with electron transport layer3Perovskite solution) to form a uniform and flat perovskite absorption layer, wherein the thickness of the perovskite absorption layer is 600nm, the perovskite absorption layer is heated on a heating table at 120 ℃ for 45min, then the prepared reduced graphene oxide solution is coated on the perovskite absorption layer, vacuum drying is carried out to obtain a reduced graphene oxide layer with the thickness of 2nm, then spin coating is carried out to obtain a spiro as a hole transport layer, the thickness of the hole transport layer is 200nm, the spin coating rotation speed is 1000, 2000, 3000, 4000 and 5000r/min, the acceleration is 1000r/min, the spin coating time is 30s, the processes from vacuum evaporation of the perovskite absorption layer to spin coating of the hole transport layer are carried out in an inert atmosphere, the prepared film is vacuum dried, the drying temperature is 80 ℃, and the drying time is 25 min;
preparation of four-semitransparent conductive electrode
And spraying the prepared nano silver wire dispersion liquid on a hole transport layer, spraying for 2 seconds, heating the hole transport layer on a hot table in the coating process, heating the hole transport layer at 100 ℃ for 10 minutes to form a nano silver wire electrode with the thickness of 20nm, drying, and finally coating the reduced graphene oxide dispersion liquid on the silver electrode by a coating instrument in a scraping mode to prepare a reduced graphene oxide layer with the thickness of 0.5nm, so that the semitransparent perovskite solar cell electrode is obtained.
As shown in fig. 1, which is an efficiency & transmittance graph of a battery device prepared by spin-coating a spiro at different rotation speeds, two curves in the graph respectively represent battery efficiency and average transmittance at different rotation speeds of the spiro, it can be seen from fig. 1 that the transmittance increases with the increase of the thickness of the hole transport layer, but the thickness of the hole transport layer itself affects the transmittance after the thickness reaches a certain value, and the transmittance is the highest at a spin-coating rotation speed of 2000r/min, which can reach 26.8%, but the battery efficiency significantly drops, and the efficiency is the most beneficial at 3000r/min and the transmittance is higher. FIG. 2 is an external quantum efficiency graph of a battery device prepared by spin-coating spiro under different rotation speed conditions, and from an external quantum efficiency curve, the photon and electron conversion capacities under other rotation speed conditions except 2000r/min are not greatly different. In conclusion, when the spin coating speed of the hole transport layer is 3000r/min, the thickness of the hole transport layer is 200nm, the transmittance is 25.8%, the preparation requirement of the semitransparent battery is met, and the photoelectric performance of the battery is the best.
Example 2
The embodiment provides a preparation method of a semitransparent perovskite solar cell electrode, which comprises the following steps:
preparation of reduced graphene oxide solution
Dissolving graphene oxide powder prepared by a Hummers method in pure water to obtain a graphene oxide aqueous solution with the concentration of 0.3 g/L, adding hydrazine hydrate for reduction, filtering and washing for 2-5 times, dissolving in isopropanol, and performing ultrasonic dispersion (the ultrasonic dispersion temperature is 25 ℃, the frequency is 500Hz, and the flow rate is 2.5 m)3The ultrasonic dispersion time is 5 hours), and reduced graphene oxide solution with the concentration of 0.2 g/L is obtained;
preparation of nano silver wire dispersion liquid
Heating 120m L ethylene glycol in oil bath pan to 180 deg.C, maintaining the temperature for 40min, and adding AgNO3The ethylene glycol solution (20m L, concentration is 0.3 mol/L), then the ethylene glycol solution (0.6 mol/L) of 20m L PVP is continuously added through a constant flow pump, the adding speed is 2m L/min, the reaction is continued for 20min after the adding is finished, a centrifugal machine is used for purifying through ethanol after the reaction is finished to obtain nano silver wires, and the nano silver wires are dispersed into isopropanol to obtain nano silver wire dispersion liquid with concentration of 5mg/m L;
third, battery interface treatment
The filtered perovskite precursor solution (0.65 mol/L MAPbI) was applied to the FTO glass surface covered with an electron transport layer by vacuum extrusion3Perovskite solution) to form a uniform and flat perovskite absorption layer with the thickness of 900nm, heating the perovskite absorption layer on a hot bench at the temperature of 80 ℃ for 60min, then coating the reduced graphene oxide solution on the perovskite absorption layer, and drying the perovskite absorption layer in vacuum to obtain a reduced graphene oxide layer with the thickness of 1.5nmCarrying out spin coating on an original graphene oxide layer to serve as a hole transport layer, wherein the thickness of the hole transport layer is 300nm, the spin coating rotating speed is 3000r/min, the acceleration is 1000r/min, the spin coating time is 30s, the whole process is placed in an inert gas atmosphere, and the prepared thin film is dried in vacuum at the drying temperature of 80 ℃ for 25 min;
preparation of four-semitransparent conductive electrode
And spraying the prepared nano-silver wire dispersion liquid on a hole transport layer, spraying for 3 seconds, heating the hole transport layer on a hot table in the coating process, heating the hole transport layer at 120 ℃ for 5 minutes to form a 30nm nano-silver electrode, finally, spin-coating the reduced graphene oxide solution on the silver electrode to form a nano-silver wire protection layer, wherein the thickness of the reduced graphene oxide layer is 1.5nm, and the reduced graphene oxide layer is coated on the silver electrode by spin-coating with a 0.3 g/L graphene oxide aqueous solution (prepared in the first half part of the step) to form a graphene oxide layer for comparison, and the thickness of the graphene oxide layer is 0.3 nm.
As shown in fig. 3, which is a graph comparing efficiency curves of battery devices prepared by respectively using Graphene Oxide (GO) and reduced graphene oxide (rGO) as the nano silver wire protection layers, it can be seen from fig. 3 that the battery efficiency of the battery prepared by reducing graphene oxide is 13.69% at most, and the battery efficiency of graphene oxide is 12.6% at most. Fig. 4 is an external quantum efficiency diagram of a battery device prepared from Graphene Oxide (GO) and reduced graphene oxide (rGO), and it can be seen from an external quantum efficiency curve that the battery device prepared from reduced graphene oxide has high electron and photon conversion efficiency and better overall battery performance.
Example 3
The embodiment provides a preparation method of a semitransparent perovskite solar cell electrode, which comprises the following steps:
preparation of reduced graphene oxide solution
Dissolving graphene oxide powder prepared by a Hummers method in pure water to obtain a graphene oxide aqueous solution with the concentration of 0.3 g/L, adding hydrazine hydrate for reduction, filtering and washing for 3 times, dissolving in isopropanol, and performing ultrasonic dispersion (the ultrasonic dispersion temperature is 25 ℃, the frequency is 500Hz, and the flow rate is 2.5 m)3H, ultrasonic dispersion time is 5h), the obtained concentration is 02 g/L of reduced graphene oxide solution;
preparation of nano silver wire dispersion liquid
Heating 110m L ethylene glycol in oil bath pan to 160 deg.C, maintaining the temperature for 50min, and adding AgNO3The ethylene glycol solution (30m L, concentration is 0.2 mol/L), then the ethylene glycol solution (0.5 mol/L) of 30m L PVP is continuously added through a constant flow pump, the adding speed is 5m L/min, the reaction is continued for 15min after the addition is finished, a centrifugal machine is used for purifying through ethanol after the reaction is finished to obtain nano silver wires, and the nano silver wires are dispersed into isopropanol to obtain nano silver wire dispersion liquid with the concentration of 3mg/m L;
third, battery interface treatment
Vacuum evaporation of filtered perovskite precursor solution (0.65 mol/L MAPbI) on FTO glass surface covered with electron transport layer3Perovskite solution) to form a uniform and flat perovskite absorption layer, the thickness of the perovskite absorption layer is 900nm, the perovskite absorption layer is heated at 110 ℃ for 55min, then the reduced graphene oxide solution is coated on the perovskite absorption layer, the reduced graphene oxide layer with the thickness of 1.5nm is obtained by vacuum drying, then spiro is coated on the perovskite absorption layer to serve as a hole transport layer, the rotating speed of the coating is 3000r/min, the acceleration is 1000r/min, the coating time is 30s, the whole process is placed in an inert gas atmosphere, the drying temperature of the prepared film in vacuum is 80 ℃, and the drying time is 25 min;
preparation of four-semitransparent conductive electrode
And spraying the prepared nano-silver wire dispersion liquid on a hole transport layer for 2-5 seconds, heating the perovskite battery on a hot table in the coating process, heating for 10min at 100 ℃ to form a nano-silver electrode of 20-50nm, and finally coating the reduced graphene oxide solution on the silver electrode in a scraping manner, wherein the thickness of the reduced graphene oxide layer is 1.5 nm.
As shown in fig. 5, which is a graph of transmittance of battery electrodes with different thicknesses prepared by different spraying amounts, and fig. 6, which is a graph of average transmittance and sheet resistance of battery electrodes with different thicknesses prepared by different spraying amounts, it can be seen from fig. 5 and fig. 6 that as the spraying amount increases, the transmittance of the battery continuously decreases, the sheet resistance continuously increases, and the average transmittance of the battery electrode with a thickness of 30nm can reach 84%, and the sheet resistance is 30 Ω/sq, so that the requirements of the translucent battery can be met, and the comprehensive performance is the best.
Example 4
The embodiment provides a preparation method of a semitransparent perovskite solar cell electrode, which comprises the following steps:
preparation of reduced graphene oxide solution
Dissolving graphene oxide powder prepared by a Hummers method in pure water to obtain a graphene oxide aqueous solution with the concentration of 0.3 g/L, adding hydrazine hydrate for reduction, filtering and washing for 5 times, dissolving in isopropanol, and performing ultrasonic dispersion (the ultrasonic dispersion temperature is 25 ℃, the frequency is 500Hz, and the flow rate is 2.5 m)3The ultrasonic dispersion time is 8 hours), and reduced graphene oxide solution with the concentration of 0.2 g/L is obtained;
preparation of nano silver wire dispersion liquid
Heating 100m L ethylene glycol in oil bath pan to 170 deg.C, maintaining the temperature for 60min, and adding AgNO3The ethylene glycol solution (40m L, concentration is 0.25 mol/L), then the ethylene glycol solution (0.4 mol/L) of 40m L PVP is continuously added through a constant flow pump, the adding speed is 5m L/min, the reaction is continued for 18min after the adding is finished, a centrifugal machine is used for purifying through ethanol after the reaction is finished to obtain nano silver wires, and the nano silver wires are dispersed into isopropanol to obtain nano silver wire dispersion liquid with concentration of 4mg/m L;
third, battery interface treatment
Vacuum evaporation of filtered perovskite precursor solution (0.65 mol/L MAPbI) on FTO glass surface covered with electron transport layer3Perovskite solution) to form a uniform and flat perovskite absorption layer, wherein the thickness of the perovskite absorption layer is 800nm, the perovskite absorption layer is heated for 50min at a 100 ℃ hot stage, then the reduced graphene oxide solution is coated on the perovskite absorption layer, the reduced graphene oxide layer with the thickness of 2nm is obtained by vacuum drying, then spiro is coated as an electron transmission layer, the thickness of the electron transmission layer is 300nm, the rotating speed of the coating is 1000r/min, the acceleration is 1000r/min, the coating time is 30s, the whole process is placed in an inert gas atmosphere, the drying temperature of the prepared film is 80 ℃, and the drying time is 25 min;
preparation of four-semitransparent conductive electrode
And spraying the prepared nano silver wire dispersion liquid on a hole transport layer for 4 seconds, heating the perovskite battery on a hot table in the coating process, heating for 10min at 100 ℃ to form a nano silver electrode with the thickness of 40nm, covering the reduced graphene oxide solution between a spiro and a silver wire, on the silver wire or forming a sandwich electrode structure of reduced graphene oxide-silver wire-reduced graphene oxide by adopting a tape casting coating method, wherein the thickness of the reduced graphene oxide layer is about 0.5nm, and comparing with the condition that the reduced graphene oxide is not covered (marked as a pure nano silver wire).
Fig. 7 shows the J-V curve of pure silver nanowire (AgNM), reduced graphene oxide between the spiro and silver nanowire (AgNM/rGO), reduced graphene oxide on the silver nanowire (rGO/AgNM), and the "sandwich" electrode structure of reduced graphene oxide-silver wire-reduced graphene oxide (rGO/AgNM/rGO), and fig. 7 shows that the battery efficiency of the "sandwich" electrode structure of reduced graphene oxide-silver wire-reduced graphene oxide is the highest, which can reach 14.69%. Fig. 8 is an external quantum efficiency diagram of a pure silver nanowire (AgNM), a reduced graphene oxide covered between a spiro and a silver wire (AgNM/rGO), a reduced graphene oxide covered on a silver wire (rGO/AgNM), and a "sandwich" electrode structure forming a reduced graphene oxide-silver wire-reduced graphene oxide (rGO/AgNM/rGO), and it can be seen from fig. 8 that the battery photon and electron conversion efficiency of the "sandwich" electrode structure of a reduced graphene oxide-silver wire-reduced graphene oxide is the highest. FIG. 9 is a battery stability test chart of pure silver nanowires (AgNM), reduced graphene oxide covered between spiro and silver wires (AgNM/rGO), reduced graphene oxide covered on silver wires (rGO/AgNM) and a sandwich electrode structure (rGO/AgNM/rGO) forming reduced graphene oxide-silver wires-reduced graphene oxide, it can be seen that the battery stability of the sandwich electrode structure of reduced graphene oxide-silver wires-reduced graphene oxide is the best, the efficiency can still be kept over 80% after being placed for 250h, the battery performances of other electrode structures are poor, the reduced graphene oxide is covered between spiro and silver wires and on silver wires in sequence, the performances of pure silver wires are the worst, the efficiencies are 12.9%, 12.6% and 12.28%, and the stability can only be kept 70%, 30% in sequence, About 15 percent. The sandwich electrode structure of the reduced graphene oxide-silver wire-reduced graphene oxide has the best device performance and excellent device stability under comprehensive consideration.
Claims (10)
1. A semi-transparent perovskite solar cell electrode is characterized by being prepared by the following method:
1) preparing a reduced graphene oxide solution: dissolving graphene oxide powder prepared by a Hummers method in pure water to obtain a graphene oxide aqueous solution, adding a reducing agent for reduction, filtering and washing for 2-5 times, dissolving in isopropanol, and performing ultrasonic dispersion to obtain a reduced graphene oxide solution;
2) preparing a nano silver wire dispersion liquid: heating ethylene glycol in an oil bath at 150-180 ℃, adding AgNO into the ethylene glycol after heating for 40-80 min3Continuously adding a PVP solution through a constant flow pump, wherein the adding speed is 2-5 m L/min, continuously reacting for 8-20 min after the addition is finished, separating and purifying after the reaction is finished to obtain a nano silver wire, and dispersing the nano silver wire in isopropanol to obtain a nano silver wire dispersion liquid;
3) preparing a semitransparent perovskite solar cell electrode: placing the FTO glass covered with the electron transport layer on a heating table at the temperature of 80-120 ℃, preparing a uniform and flat perovskite absorption layer on the surface, coating the reduced graphene oxide solution prepared in the step 1) on the perovskite absorption layer according to requirements, drying in vacuum to obtain a reduced graphene oxide layer, then spin-coating spiro as a hole transport layer, then coating the nano silver wire dispersion liquid obtained in the step 2) on the hole transport layer, drying to form a nano silver wire electrode, covering the reduced graphene oxide solution obtained in the step 1) between spiro and a silver wire on a hot bench, or preparing a reduced graphene oxide layer on the silver wire, or preparing the reduced graphene oxide layers on the upper and lower sides of the silver wire to form a 'sandwich' electrode structure of reduced graphene oxide-silver wire-reduced graphene oxide, so as to obtain the semi-transparent perovskite solar cell electrode.
2. The semi-transparent perovskite solar cell electrode of claim 1, wherein the reducing agent of step 1) is one of hydrazine hydrate, sodium borohydride and sodium dodecyl benzene sulfonate.
3. The semi-transparent perovskite solar cell electrode as claimed in claim 1, wherein the concentration of the graphene oxide aqueous solution in step 1) is 0.3-0.6 g/L, and the concentration of the reduced graphene oxide solution in step 1) is 0.2-0.5 g/L.
4. The translucent perovskite solar cell electrode of claim 1, wherein step 2) the AgNO3The solution is AgNO3The concentration of the ethylene glycol solution is 0.15-0.3 mol/L, and the AgNO in the step 2)3The volume ratio of the solution to the ethylene glycol is 1: 1 to 6.
5. The semi-transparent perovskite solar cell electrode as claimed in claim 1, wherein the PVP solution in step 2) is PVP glycol solution with concentration of 0.3-0.6 mol/L, and AgNO in step 2)3AgNO in solution3The molar ratio of the nano silver wire dispersion liquid to PVP in a PVP solution is 1: 1.5-2.5, and the concentration of the nano silver wire dispersion liquid in the step 2) is 2-5 mg/m L.
6. The semi-transparent perovskite solar cell electrode as claimed in claim 1, wherein the thickness of the perovskite absorption layer of step 3) is 600-900 nm.
7. The semi-transparent perovskite solar cell electrode as claimed in claim 1, wherein the spin coating in step 3) is performed at a rotating speed of 1000-5000 r/min, an acceleration of 1000r/min and a spin coating time of 30 s; and 3) the thickness of the hole transport layer in the step 3) is 100-500 nm.
8. The semi-transparent perovskite solar cell electrode as claimed in claim 1, wherein the thickness of the nano silver wire electrode in step 3) is 20-50 nm; and 3) the thickness of the reduced graphene oxide layer is less than or equal to 2 nm.
9. A method of manufacturing a translucent perovskite solar cell electrode as claimed in any one of claims 1 to 8, characterized in that the specific steps are as follows:
1) preparing a reduced graphene oxide solution: dissolving graphene oxide powder prepared by a Hummers method in pure water to obtain a graphene oxide aqueous solution, adding a reducing agent for reduction, filtering and washing for 2-5 times, dissolving in isopropanol, and performing ultrasonic dispersion to obtain a reduced graphene oxide solution;
2) preparing a nano silver wire dispersion liquid: heating ethylene glycol in an oil bath at 150-180 ℃, adding AgNO into the ethylene glycol after heating for 40-80 min3Continuously adding a PVP solution through a constant flow pump, wherein the adding speed is 2-5 m L/min, continuously reacting for 8-20 min after the addition is finished, separating and purifying after the reaction is finished to obtain a nano silver wire, and dispersing the nano silver wire in isopropanol to obtain a nano silver wire dispersion liquid;
3) preparing a semitransparent perovskite solar cell electrode: placing the FTO glass covered with the electron transport layer on a heating table at the temperature of 80-120 ℃, preparing a uniform and flat perovskite absorption layer on the surface, coating the reduced graphene oxide solution prepared in the step 1) on the perovskite absorption layer according to requirements, drying in vacuum to obtain a reduced graphene oxide layer, then spin-coating spiro as a hole transport layer, then coating the nano silver wire dispersion liquid obtained in the step 2) on the hole transport layer, drying to form a nano silver wire electrode, covering the reduced graphene oxide solution obtained in the step 1) between spiro and a silver wire on a hot bench, or preparing a reduced graphene oxide layer on the silver wire, or preparing the reduced graphene oxide layers on the upper and lower sides of the silver wire to form a 'sandwich' electrode structure of reduced graphene oxide-silver wire-reduced graphene oxide, so as to obtain the semi-transparent perovskite solar cell electrode.
10. A translucent perovskite solar cell prepared from the translucent perovskite solar cell electrode according to any one of claims 1 to 8.
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