CN109545969A - A kind of lithium, silver are co-doped with nickel oxide film and its application in perovskite solar cell - Google Patents

A kind of lithium, silver are co-doped with nickel oxide film and its application in perovskite solar cell Download PDF

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CN109545969A
CN109545969A CN201811227041.9A CN201811227041A CN109545969A CN 109545969 A CN109545969 A CN 109545969A CN 201811227041 A CN201811227041 A CN 201811227041A CN 109545969 A CN109545969 A CN 109545969A
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silver
perovskite
lithium
colored
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CN109545969B (en
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李璠
夏雪峰
王晓峰
江奕华
邹敏华
彭家奕
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Nanchang University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/10—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising heterojunctions between organic semiconductors and inorganic semiconductors
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

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Abstract

The present invention provides the preparation method and applications of a kind of perovskite solar cell lithium, silver-colored co-doped nickel oxide nanoparticle.By weighing a certain amount of Ni (NO3)2·6H2O、LiNO3And AgNO3Stirring and dissolving in deionized water is added, its molar ratio range is 0.989~0.98:0.001~0.005:0.01~0.015, then NaOH solution is added dropwise, until pH to 9.8~10, after washing and drying, the nanoparticle of lithium, silver-colored co-doped nickel oxide is obtained by 270 DEG C of calcinings.Nanoparticle is prepared into solution, is applied to perovskite solar battery as hole transmission layer.The present invention can effectively improve the photoelectric conversion efficiency of perovskite battery.

Description

A kind of lithium, silver are co-doped with nickel oxide film and its application in perovskite solar cell
Technical field
The present invention relates to a kind of lithium, silver to be co-doped with nickel oxide film and its application in perovskite solar cell, belongs to new Materials for solar cells technical field.
Background technique
Hybrid inorganic-organic perovskite material possesses superior charge transport quality, carrier diffusion distance, Quan Guangpu The advantages such as absorption and high absorptivity, this allows this material to effectively absorb sunlight, and efficiently produces photoproduction load Stream, while reducing the energy loss in photoelectric conversion process.Solar-electricity based on hybrid inorganic-organic perovskite material Pond causes the extensive concern of people due to the fast lifting of its efficiency.Since two thousand nine, efficiency is increased from 3.8% 22% or more, become most active field in current novel solar battery research.
Nickel oxide (NiOx) Yin Qiyi preparation, outstanding advantages of level-density parameter is used as reversed plane perovskite solar energy The hole transmission layer of battery is studied extensively.In numerous synthesis NiOxMethod in, NiO that solution at room temperature method is preparedxNanometer Particle is heat-treated when applying in battery device without additional annealing, this is greatly expanded NiOxApplication range, such as For flexible device.But due to pure NiOxConductivity itself is not high enough, therefore, improves NiOxConductivity to improve its performance with And cell conversion efficiency is of great significance.
Summary of the invention
The object of the present invention is to provide the preparations of a kind of perovskite solar cell lithium, silver-colored co-doped nickel oxide nanoparticle Method, with solution at room temperature method synthesis lithium, silver-colored codope NiOxNanoparticle.
It is a further object to provide lithium, silver-colored co-doped nickel oxide nanoparticles in the reversed plane perovskite sun The application of the hole transmission layer of energy battery, to improve its photoelectric conversion efficiency.
The present invention is achieved by the following technical solutions:
The preparation method of a kind of perovskite solar cell lithium, silver-colored co-doped nickel oxide nanoparticle of the invention, including Following steps:
(1) a certain amount of Ni (NO is weighed respectively3)2·6H2O、LiNO3And AgNO3Stirring and dissolving in deionized water is added, Molar ratio range is 0.989~0.98:0.001~0.005:0.01~0.015, then weighs a certain amount of NaOH and be dissolved in water, is prepared Concentration is the NaOH solution of 9~10mol/L.
(2) NaOH solution is slowly dropped to Ni (NO3)2·6H2O、LiNO3And AgNO3Solution in, until pH to 9.8 When~10, stop being added dropwise, obtains green suspension, and stir 5~10 minutes.
(3) gained suspension is filtered and is precipitated, then precipitating is distributed in deionized water, this step repeats three times.
(4) precipitating after cleaning is put into crucible, and 60~80 DEG C of 6~8 hours of vacuum drying, obtains green solid, then Crucible is put into Muffle furnace and is calcined 2~3 hours for 265~275 DEG C, black lithium, silver-colored codope NiO are obtainedxNanoparticle powder End is used after giving over to.
Ni (NO in step (1)3)2·6H2O、LiNO3And AgNO3Mole summation of three is 1.
The application of a kind of lithium of the present invention, silver-colored co-doped nickel oxide nanoparticle in perovskite solar cell, packet Include following steps:
(1) electro-conductive glass etched electrically conducting transparent ito glass substrate processing: is used into glass cleaner, deionization respectively Water, acetone, isopropanol are ultrasonically treated 15 minutes, then are dried up substrate with nitrogen gun, and ultraviolet irradiation is handled ten minutes.
(2) lithium, silver-colored codope NiOxNanoparticulate thin films preparation: by lithium obtained, silver-colored codope NiOxNanoparticle powder It is dissolved in deionized water, ultrasound 15~30 minutes, spin-coating film.
(3) preparation of perovskite thin film precursor solution: by PbI2And CH3NH3I, which is dissolved according to molar ratio for 1:1, to be contained There is in n,N-Dimethylformamide (DMF) solution of dimethyl sulfoxide (DMSO) (volume ratio of DMSO and DMF are 1:4), in room Temperature is lower to stir 12h.
(4) prepared by perovskite active layer: the perovskite precursor solution prepared is spin-coated on lithium, silver-colored codope NiOxIt receives Nanoparticle thin film surface is heated 1~3 minute using 60~65 DEG C, and 95~100 DEG C of heating obtain perovskite activity for 10 minutes Layer.
(5) preparation of electron transfer layer: with the revolving speed spin coating concentration of 1500rpm being 25mg/ml on perovskite thin film surface Fullerene derivate PCBM chlorobenzene solution.Later on the surface PCBM with the revolving speed spin coating 2,9- dimethyl -4,7- two of 5000rpm Phenyl -1,10- ferrosin (BCP) methanol saturated solution.
(6) preparation of Ag electrode: the Ag electrode with a thickness of 150~200nm is obtained with thermal evaporation deposition, obtains complete calcium titanium Mine solar cell device.
PbI in step (3)2Molar concentration be 0.88-1.2M；
It is proposed that the NiO nanoparticle being co-doped with solution at room temperature method synthesis lithium, silver, and it is applied to perovskite The hole transmission layer of solar battery, this method can effectively by the photoelectric conversion efficiency of perovskite solar battery from 10.58% is increased to 16.38%.
Detailed description of the invention
Fig. 1 is the undoped NiO of solution at room temperature method preparationxThe stereoscan photograph of nanoparticulate thin films.
Fig. 2 is the lithium of solution at room temperature method of the present invention preparation, silver-colored codope NiOxThe stereoscan photograph of nanoparticulate thin films.
Fig. 3 is of the invention using lithium, the NiO of silver-colored codopexThe calcium that nanoparticulate thin films are prepared as hole transmission layer The undoped NiO of titanium ore solar battery and usexThe perovskite sun that nanoparticulate thin films are prepared as hole transmission layer The I-V performance of energy battery compares.
Specific embodiment
The present invention is further described in detail with reference to the accompanying drawings and examples.
Embodiment 1:
Lithium, silver-colored codope NiOxThe synthesis of nanoparticle.
(1) Ni (NO that molar ratio is 0.98:0.005:0.015 is weighed respectively3)2·6H2O、LiNO3And AgNO3Addition is gone Stirring and dissolving in ionized water, then weigh a certain amount of NaOH and be dissolved in water, compound concentration is the NaOH solution of 10mol/L.
(2) NaOH solution is slowly dropped to Ni (NO3)2·6H2O、LiNO3And AgNO3Solution in, until pH to 10 When, stop being added dropwise.Green suspension is obtained, and is stirred 5 minutes.
(3) gained suspension is filtered and is precipitated, then precipitating is distributed in deionized water, this step repeats three times.
(4) precipitating after cleaning is put into crucible, and 80 DEG C are dried in vacuo 6 hours, obtain green solid, then crucible is put into It is calcined 2 hours for 270 DEG C in Muffle furnace, obtains black lithium, silver-colored codope NiOxNanoparticle powder, used after giving over to.
As depicted in figs. 1 and 2, respectively NiOxNanoparticulate thin films and lithium, Ag doping NiOxNanoparticulate thin films, can be with Find out that the nano particle diameter formed after lithium, silver-colored codope is smaller, can be more effectively dispersed in solution, the film of formation is also more Add uniformly.
The preparation of perovskite solar cell device.
(1) electro-conductive glass etched electrically conducting transparent ito glass substrate processing: is used into glass cleaner, deionization respectively Water, acetone, isopropanol are ultrasonically treated 15 minutes, then are dried up substrate with nitrogen gun, and ultraviolet irradiation is handled ten minutes.
(2) lithium, silver-colored codope NiOxNanoparticulate thin films preparation: by lithium obtained, silver-colored codope NiOxNanoparticle powder It is dissolved in deionized water, ultrasound 15 minutes, spin-coating film.
(3) preparation of perovskite thin film precursor solution: by PbI2And CH3NH3I is 1:1, PbI according to molar ratio2's Molar concentration is 0.88M-1.2M, is dissolved in the n,N-Dimethylformamide containing dimethyl sulfoxide (DMSO) (DMF) solution (volume ratio of DMSO and DMF are 1:4), is stirred at room temperature 12h.
(4) prepared by perovskite active layer: the perovskite precursor solution prepared is spin-coated on lithium, silver-colored codope NiOxIt receives Nanoparticle thin film surface is heated 1~3 minute using 60~65 DEG C, and 95~100 DEG C of heating obtain perovskite activity for 10 minutes Layer.
(5) preparation of electron transfer layer: with the revolving speed spin coating concentration of 1500rpm being 25mg/ml on perovskite thin film surface Fullerene derivate PCBM chlorobenzene solution.Later on the surface PCBM with the revolving speed spin coating 2,9- dimethyl -4,7- two of 5000rpm Phenyl -1,10- ferrosin (BCP) methanol saturated solution.
(6) preparation of Ag electrode: the Ag electrode with a thickness of 150~200nm is obtained with thermal evaporation deposition, obtains complete calcium titanium Mine solar cell device.
As shown in figure 3, being based on lithium, Ag doping NiOxBattery device short circuit current afterwards is significantly improved, thus effectively Improve the incident photon-to-electron conversion efficiency of perovskite solar battery.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include Within protection scope of the present invention.

Claims (2)

1. a kind of perovskite solar cell lithium, silver-colored co-doped nickel oxide nanoparticle, it is characterised in that: the preparation method is as follows:
(1) a certain amount of Ni (NO is weighed respectively3)2·6H2O、LiNO3And AgNO3Stirring and dissolving in deionized water is added, mole It is 0.989~0.98:0.001~0.005:0.01~0.015 than range, then weighs a certain amount of NaOH and be dissolved in water, compound concentration For the NaOH solution of 9~10mol/L；
(2) NaOH solution is slowly dropped to Ni (NO3)2·6H2O、LiNO3And AgNO3Solution in, until pH to 9.8~10 When, stop being added dropwise, obtains green suspension, and stir 5~10 minutes；
(3) gained suspension is filtered and is precipitated, then precipitating is distributed in deionized water, this step repeats three times；
(4) precipitating after cleaning is put into crucible, and 60~80 DEG C of 6~8 hours of vacuum drying, obtains green solid, then by earthenware Crucible is put into Muffle furnace and calcines 2~3 hours for 265~275 DEG C, obtains black lithium, silver-colored codope NiOxNanoparticle powder, stay After being used as；
Ni (NO in step (1)3)2·6H2O、LiNO3And AgNO3Mole summation of three is 1.
2. a kind of perovskite solar cell lithium as described in claim 1, silver-colored co-doped nickel oxide nanoparticle are in perovskite Application in solar cell, it is characterised in that: steps are as follows:
(1) electro-conductive glass etched electrically conducting transparent ito glass substrate processing: is used into glass cleaner, deionized water, third respectively Ketone, isopropanol are ultrasonically treated 15 minutes, then are dried up substrate with nitrogen gun, and ultraviolet irradiation is handled ten minutes；
(2) lithium, silver-colored codope NiOxNanoparticulate thin films preparation: by lithium obtained, silver-colored codope NiOxNanoparticle powder is dissolved in Deionized water, ultrasound 15~30 minutes, spin-coating film；
(3) preparation of perovskite thin film precursor solution: by PbI2And CH3NH3I is that 1:1 is dissolved in containing two according to molar ratio In n,N-Dimethylformamide (DMF) solution of methyl sulfoxide (DMSO) (volume ratio of DMSO and DMF are 1:4), at room temperature Stir 12h；
(4) prepared by perovskite active layer: the perovskite precursor solution prepared is spin-coated on lithium, silver-colored codope NiOxNanoparticle Sub- film surface heats 1~3 minute using 60~65 DEG C, and 95~100 DEG C of heating obtain perovskite active layer in 10 minutes；
(5) preparation of electron transfer layer: with the revolving speed spin coating concentration of 1500rpm being the richness of 25mg/ml on perovskite thin film surface Strangle ene derivative PCBM chlorobenzene solution；Later on the surface PCBM with the revolving speed spin coating 2,9- dimethyl -4,7- hexichol of 5000rpm Base -1,10- ferrosin (BCP) methanol saturated solution；
(6) preparation of Ag electrode: the Ag electrode with a thickness of 150~200nm is obtained with thermal evaporation deposition, obtains complete perovskite too Positive energy battery device；
PbI in step (3)2Molar concentration be 0.88-1.2M.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110735160A (en) * 2019-05-10 2020-01-31 湖北大学 Preparation method of up-conversion fluorescent anti-counterfeiting labels

Citations (3)

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Publication number Priority date Publication date Assignee Title
CN102392237A (en) * 2011-10-26 2012-03-28 东北大学 Preparation method for Ag-Li co-doped zinc oxide film
WO2013106836A1 (en) * 2012-01-13 2013-07-18 The Regents Of The University Of California Metal-chalcogenide photovoltaic device with metal-oxide nanoparticle window layer
CN108054282A (en) * 2017-11-27 2018-05-18 济南大学 Zinc doping nickel oxide nanoparticle hole transmission layer inverts perovskite solar cell and preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102392237A (en) * 2011-10-26 2012-03-28 东北大学 Preparation method for Ag-Li co-doped zinc oxide film
WO2013106836A1 (en) * 2012-01-13 2013-07-18 The Regents Of The University Of California Metal-chalcogenide photovoltaic device with metal-oxide nanoparticle window layer
CN108054282A (en) * 2017-11-27 2018-05-18 济南大学 Zinc doping nickel oxide nanoparticle hole transmission layer inverts perovskite solar cell and preparation method

Non-Patent Citations (1)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110735160A (en) * 2019-05-10 2020-01-31 湖北大学 Preparation method of up-conversion fluorescent anti-counterfeiting labels
CN110735160B (en) * 2019-05-10 2021-06-11 湖北大学 Preparation method of up-conversion fluorescent anti-counterfeiting label

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