CN109545969B - Lithium and silver co-doped nickel oxide film and application thereof in perovskite solar cell - Google Patents
Lithium and silver co-doped nickel oxide film and application thereof in perovskite solar cell Download PDFInfo
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- CN109545969B CN109545969B CN201811227041.9A CN201811227041A CN109545969B CN 109545969 B CN109545969 B CN 109545969B CN 201811227041 A CN201811227041 A CN 201811227041A CN 109545969 B CN109545969 B CN 109545969B
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Abstract
The invention provides a perovskite solar cellA preparation method and application of a cell lithium and silver co-doped nickel oxide nano particle. By weighing a certain amount of Ni (NO)3)2·6H2O、LiNO3And AgNO3Adding the mixture into deionized water, stirring and dissolving the mixture, wherein the molar ratio of the mixture to the deionized water is 0.989-0.98: 0.001-0.005: 0.01-0.015, then dropwise adding a NaOH solution until the pH value is 9.8-10, washing and drying the mixture, and calcining the mixture at 270 ℃ to obtain the lithium and silver codoped nickel oxide nanoparticles. And preparing a solution from the nano particles, and applying the solution as a hole transport layer to the perovskite solar cell. The invention can effectively improve the photoelectric conversion efficiency of the perovskite battery.
Description
Technical Field
The invention relates to a lithium and silver co-doped nickel oxide film and application thereof in a perovskite solar cell, belonging to the technical field of new material solar cells.
Background
The organic-inorganic hybrid perovskite material has the advantages of excellent charge transmission property, long carrier diffusion distance, full spectrum absorption, high light absorption coefficient and the like, so that the material can effectively absorb sunlight, efficiently generate photon-generated carriers and simultaneously reduce energy loss in the photoelectric conversion process. Solar cells based on organic-inorganic hybrid perovskite materials have attracted much attention due to their rapid increase in efficiency. Since 2009, the efficiency of solar cells has increased from 3.8% to over 22%, and the solar cells are the most active field in the research of new solar cells.
Nickel oxide (NiO)x) The hole transport layer of the perovskite solar cell is widely researched due to the outstanding advantages of easy preparation, energy level matching and the like. In the synthesis of NiOxIn the method, NiO prepared by a room-temperature solution methodxThe nano particles do not need additional annealing heat treatment when being applied to a battery device, so that NiO is greatly expandedxFor example for flexible devices. But because of pure NiOxThe conductivity itself is not sufficiently high, and therefore, NiO is improvedxTo improve the conductivity ofThe energy and the battery conversion efficiency have important significance.
Disclosure of Invention
The invention aims to provide a preparation method of lithium and silver codoped nickel oxide nanoparticles for a perovskite solar cell, which is characterized in that lithium and silver codoped NiO is synthesized by a room-temperature solution methodxNanoparticles.
The invention also aims to provide application of the lithium and silver co-doped nickel oxide nano particles in a hole transport layer of a reverse planar perovskite solar cell so as to improve the photoelectric conversion efficiency of the reverse planar perovskite solar cell.
The invention is realized by the following technical scheme:
the invention discloses a preparation method of lithium and silver co-doped nickel oxide nanoparticles for a perovskite solar cell, which comprises the following steps:
(1) respectively weighing a certain amount of Ni (NO)3)2·6H2O、LiNO3And AgNO3Adding the mixture into deionized water, stirring and dissolving the mixture, wherein the molar ratio of the mixture is 0.989-0.98: 0.001-0.005: 0.01-0.015, and then weighing a certain amount of NaOH to dissolve the NaOH in water to prepare a NaOH solution with the concentration of 9-10 mol/L.
(2) Slowly drop NaOH solution to Ni (NO)3)2·6H2O、LiNO3And AgNO3And (3) stopping dropwise adding until the pH value reaches 9.8-10 to obtain a green suspension, and stirring for 5-10 minutes.
(3) And carrying out suction filtration on the obtained suspension to obtain a precipitate, dispersing the precipitate into deionized water, and repeating the step for three times.
(4) Putting the cleaned precipitate into a crucible, vacuum-drying the precipitate at the temperature of 60-80 ℃ for 6-8 hours to obtain a green solid, putting the crucible into a muffle furnace, calcining the crucible at the temperature of 265-275 ℃ for 2-3 hours to obtain black lithium and silver codoped NiOxThe nanoparticle powder of (4) is left for later use.
Ni (NO) in step (1)3)2·6H2O、LiNO3And AgNO3The molar sum of the three is 1.
The application of the lithium and silver co-doped nickel oxide nano particles in the perovskite solar cell comprises the following steps:
(1) processing a transparent conductive ITO glass substrate: and (3) respectively carrying out ultrasonic treatment on the etched conductive glass for 15 minutes by using a glass cleaning agent, deionized water, acetone and isopropanol, then carrying out blow-drying on the substrate by using a nitrogen gun, and carrying out ultraviolet irradiation treatment for ten minutes.
(2) Lithium and silver co-doped NiOxPreparing a nano particle film: the prepared lithium and silver co-doped NiOxDissolving the nano particle powder in deionized water, performing ultrasonic treatment for 15-30 minutes, and performing spin coating to form a film.
(3) Preparing a perovskite film precursor solution: will PbI2And CH3NH3I is dissolved in N, N-Dimethylformamide (DMF) containing dimethyl sulfoxide (DMSO) according to a molar ratio of 1:1 (volume ratio of DMSO to DMF is 1:4), and stirred at room temperature for 12 h.
(4) Preparing a perovskite active layer: the prepared perovskite precursor solution is coated on the lithium and silver codoped NiOxAnd heating the surface of the nano particle film at 60-65 ℃ for 1-3 minutes and at 95-100 ℃ for 10 minutes to obtain the perovskite active layer.
(5) Preparation of an electron transport layer: spin-coating 25mg/ml fullerene derivative PCBM chlorobenzene solution on the surface of the perovskite thin film at the rotating speed of 1500 rpm. And spin-coating 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) methanol saturated solution on the surface of the PCBM at the rotating speed of 5000 rpm.
(6) Preparing an Ag electrode: and (3) obtaining an Ag electrode with the thickness of 150-200 nm by using a thermal evaporation method to obtain a complete perovskite solar cell device.
PbI in step (3)2The molar concentration of (A) is 0.88-1.2M;
the method for synthesizing the lithium-silver co-doped nickel oxide nano particles by using the room-temperature solution method and applying the lithium-silver co-doped nickel oxide nano particles to the hole transport layer of the perovskite solar cell can effectively improve the photoelectric conversion efficiency of the perovskite solar cell from 10.58% to 16.38%.
Drawings
FIG. 1 shows undoped NiO prepared by room temperature solution methodxScanning of nanoparticle thin filmsAnd (4) electron microscope photographs.
FIG. 2 shows lithium and silver co-doped NiO prepared by the room temperature solution methodxScanning electron microscope photo of the nano particle film.
FIG. 3 shows a lithium and silver co-doped NiO of the present inventionxPerovskite solar cell prepared by taking nano particle film as hole transport layer and undoped NiO adopted by perovskite solar cellxAnd comparing the I-V performance of the perovskite solar cell prepared by using the nano particle film as a hole transport layer.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1:
lithium and silver co-doped NiOxAnd (4) synthesizing the nano particles.
(1) Separately weighing Ni (NO) with a molar ratio of 0.98:0.005:0.0153)2·6H2O、LiNO3And AgNO3Adding into deionized water, stirring and dissolving, then weighing a certain amount of NaOH to dissolve in water, and preparing NaOH solution with the concentration of 10 mol/L.
(2) Slowly drop NaOH solution to Ni (NO)3)2·6H2O、LiNO3And AgNO3Until the pH reached 10, the dropwise addition was stopped. A green suspension was obtained and stirred for 5 minutes.
(3) And carrying out suction filtration on the obtained suspension to obtain a precipitate, dispersing the precipitate into deionized water, and repeating the step for three times.
(4) Putting the cleaned precipitate into a crucible, vacuum-drying at 80 ℃ for 6 hours to obtain a green solid, and putting the crucible into a muffle furnace to calcine at 270 ℃ for 2 hours to obtain black lithium and silver codoped NiOxThe nanoparticle powder of (4) is left for later use.
NiO as shown in FIG. 1 and FIG. 2xNano particle film and lithium and silver doped NiOxThe nano particle film has the advantages that the particle size of nano particles formed after the co-doping of lithium and silver is smaller, the nano particles can be effectively dispersed in a solution, and the formed film is more uniform.
And (3) preparation of the perovskite solar cell device.
(1) Processing a transparent conductive ITO glass substrate: and (3) respectively carrying out ultrasonic treatment on the etched conductive glass for 15 minutes by using a glass cleaning agent, deionized water, acetone and isopropanol, then carrying out blow-drying on the substrate by using a nitrogen gun, and carrying out ultraviolet irradiation treatment for ten minutes.
(2) Lithium and silver co-doped NiOxPreparing a nano particle film: the prepared lithium and silver co-doped NiOxDissolving the nano particle powder in deionized water, performing ultrasonic treatment for 15 minutes, and performing spin coating to form a film.
(3) Preparing a perovskite film precursor solution: will PbI2And CH3NH3I is 1:1 according to the molar ratio, PbI2Was dissolved in N, N-Dimethylformamide (DMF) solution containing dimethyl sulfoxide (DMSO) (volume ratio of DMSO to DMF is 1:4), and stirred at room temperature for 12 h.
(4) Preparing a perovskite active layer: the prepared perovskite precursor solution is coated on the lithium and silver codoped NiOxAnd heating the surface of the nano particle film at 60-65 ℃ for 1-3 minutes and at 95-100 ℃ for 10 minutes to obtain the perovskite active layer.
(5) Preparation of an electron transport layer: spin-coating 25mg/ml fullerene derivative PCBM chlorobenzene solution on the surface of the perovskite thin film at the rotating speed of 1500 rpm. And spin-coating 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP) methanol saturated solution on the surface of the PCBM at the rotating speed of 5000 rpm.
(6) Preparing an Ag electrode: and (3) obtaining an Ag electrode with the thickness of 150-200 nm by using a thermal evaporation method to obtain a complete perovskite solar cell device.
As shown in figure 3, based on lithium and silver doped NiOxThe short-circuit current of the battery device is obviously improved, so that the photoelectric conversion efficiency of the perovskite solar battery is effectively improved.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (1)
1. The preparation method of the lithium and silver co-doped nickel oxide nanoparticle hole transport layer perovskite solar cell is characterized by comprising the following steps of:
(1) respectively weighing a certain amount of Ni (NO)3)2·6H2O、LiNO3And AgNO3Adding the mixture into deionized water, stirring and dissolving the mixture, wherein the molar ratio of the mixture is 0.989-0.98: 0.001-0.005: 0.01-0.015, and then weighing a certain amount of NaOH to dissolve the NaOH in water to prepare a NaOH solution with the concentration of 9-10 mol/L;
(2) slowly drop NaOH solution to Ni (NO)3)2·6H2O、LiNO3And AgNO3The dropwise adding is stopped until the pH value reaches 9.8-10 to obtain a green suspension, and the green suspension is stirred for 5-10 minutes;
(3) carrying out suction filtration on the obtained suspension to obtain a precipitate, dispersing the precipitate into deionized water, and repeating the step for three times;
(4) putting the cleaned precipitate into a crucible, vacuum-drying the precipitate at the temperature of 60-80 ℃ for 6-8 hours to obtain a green solid, putting the crucible into a muffle furnace, calcining the crucible at the temperature of 265-275 ℃ for 2-3 hours to obtain black lithium and silver codoped NiOxThe nanoparticle powder of (4) is left for later use;
ni (NO) in step (1)3)2·6H2O、LiNO3And AgNO3The sum of the molar ratio of the three is 1;
the perovskite solar cell is prepared by the following steps:
(1) processing a transparent conductive ITO glass substrate: respectively carrying out ultrasonic treatment on the etched conductive glass for 15 minutes by using a glass cleaning agent, deionized water, acetone and isopropanol, then blowing the substrate dry by using a nitrogen gun, and carrying out ultraviolet irradiation treatment for ten minutes;
(2) lithium and silver co-doped NiOxPreparing a nanoparticle hole transport layer: the prepared lithium and silver co-doped NiOxDissolving the nano particle powder in deionized water, performing ultrasonic treatment for 15-30 minutes, and performing spin coating to form a film;
(3) before perovskite filmPreparing a body solution: will PbI2And CH3NH3Dissolving I in N, N-dimethylformamide solution containing dimethyl sulfoxide according to the molar ratio of 1:1, wherein the volume ratio of the dimethyl sulfoxide to the N, N-dimethylformamide is 1:4, and stirring at room temperature for 12 hours;
(4) preparing a perovskite active layer: the prepared perovskite precursor solution is coated on the lithium and silver codoped NiOxHeating the surface of the nano particle hole transport layer at 60-65 ℃ for 1-3 minutes and at 95-100 ℃ for 10 minutes to obtain a perovskite active layer;
(5) preparation of an electron transport layer: spin-coating a fullerene derivative PCBM chlorobenzene solution with the concentration of 25mg/ml on the surface of the perovskite thin film at the rotating speed of 1500 rpm; then spin-coating 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline methanol saturated solution on the surface of the PCBM at the rotating speed of 5000 rpm;
(6) preparing an Ag electrode: obtaining an Ag electrode with the thickness of 150-200 nm by using a thermal evaporation method to obtain a complete perovskite solar cell device;
PbI in step (3)2The molar concentration of (B) is 0.88-1.2M.
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