CN109244251A - A kind of perovskite solar battery and preparation method thereof adulterating potassium rhodanide - Google Patents

A kind of perovskite solar battery and preparation method thereof adulterating potassium rhodanide Download PDF

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CN109244251A
CN109244251A CN201810988707.6A CN201810988707A CN109244251A CN 109244251 A CN109244251 A CN 109244251A CN 201810988707 A CN201810988707 A CN 201810988707A CN 109244251 A CN109244251 A CN 109244251A
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perovskite
solution
layer
potassium rhodanide
adulterating
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闫小琴
张汝晓
李明华
席家豪
王贯勇
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Guizhou Zhongshui Material Technology Co Ltd
University of Science and Technology Beijing USTB
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Guizhou Zhongshui Material Technology Co Ltd
University of Science and Technology Beijing USTB
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
    • H10K30/30Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation comprising bulk heterojunctions, e.g. interpenetrating networks of donor and acceptor material domains
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10Deposition of organic active material
    • H10K71/12Deposition of organic active material using liquid deposition, e.g. spin coating
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00Constructional details relating to the organic devices covered by this subclass
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract

Perovskite area of solar cell belonging to the present invention provides a kind of perovskite solar battery and preparation method thereof for adulterating potassium rhodanide.Involved its structure of perovskite battery is respectively FTO electro-conductive glass, electron transfer layer, perovskite light-absorption layer, hole transmission layer and metal electrode from bottom to up.Present invention seek to address that perovskite crystalline difference and perovskite battery lag larger problem.Method by adulterating potassium rhodanide in perovskite light-absorption layer, it can change the crystallization kinetics of perovskite, promote growing up for crystal grain, it is passivated internal flaw state, and the phase structure of perovskite can be stablized, inhibit Ion transfer, so as to effectively improve the crystalline quality of perovskite, perovskite cell photoelectric efficiency and stability are improved, hysteresis effect is eliminated.

Description

A kind of perovskite solar battery and preparation method thereof adulterating potassium rhodanide
Technical field
The present invention relates to perovskite area of solar cell, in particular to a kind of perovskite solar energy for adulterating potassium rhodanide Battery and preparation method thereof.
Background technique
Currently, in area of solar cell, perovskite solar battery is due to high incident photon-to-electron conversion efficiency, low system Standby cost becomes the hot spot for falling over each other research.Organic metal halide perovskite material is as the light-absorption layer in perovskite battery, tool There are high absorptivity, carrier diffusion distance, the bipolarity charge transport quality, low exciton bind energy of length.But Since organic metal halide perovskite material is to environment sensitive is prepared, that there are crystalline qualities is poor, defect is more, mutually unstable asks Topic, to affect highlighting for perovskite material advantage, limits the promotion of perovskite battery efficiency and stability, and cause electricity The larger hysteresis effect in pond, therefore preparing the perovskite thin film of high quality and inhibiting hysteresis effect is to prepare efficient stable perovskite electricity The key in pond.
Selecting suitable substance adulterated with Ca and Ti ore is a kind of effective ways for improving perovskite crystalline quality, such as in calcium titanium Suitable plumbous rhodanate (the Pb (SCN) of doping in mine2), lead acetate (Pb (Ac)2), iodate ammonia (NH4I), ammonium thiocyanate (NH4SCN) Etc. the crystallization kinetics that can change perovskite, promote growing up for crystal grain, inhibits internal flaw state, to improve battery efficiency And stability, inhibit hysteresis effect.In addition, modifying interface method can also inhibit hysteresis effect, for example, using ionic liquid (IL), PCBM, potassium chloride (KCl) etc. are modified electron transfer layer and the interface of perovskite and can effectively passivation interface defect, inhibition carrier be answered It closes, to eliminate hysteresis effect.This patent uses the calcium titanium that perovskite doping method obtains big crystal grain size, low-defect-density Mine film layer, the perovskite battery efficiency and stability of preparation are improved, and hysteresis effect is inhibited.
Summary of the invention
The present invention is directed to propose a kind of perovskite solar battery and preparation method thereof adulterated using potassium rhodanide, it can Effectively inhibit hysteresis effect, improve perovskite battery efficiency and stability.
Perovskite solar battery structure in the present invention is as shown in Figure 1, respectively substrate of glass 1, FTO are transparent from bottom to top Electrode 2, TiO2Compacted zone 3, TiO2Mesoporous layer 4, perovskite light-absorption layer 5, Spiro-OMeTAD hole transmission layer 6, metal electrode 7;
Further, the FTO transparent electrode is to adulterate the tin oxide of fluorine, and sheet resistance is 14 Ω, light transmittance 90%;
Further, the TiO2Compacted zone is that the titanium dioxide precursor solution of configuration is spin-coated on FTO electro-conductive glass, And 30min is heated at 510 DEG C, with a thickness of 30-60nm;
Further, the TiO2Mesoporous layer is diluted commercial titanium dioxide slurry for rotary coating in TiO2On compacted zone, and 30min is heated at 510 DEG C, with a thickness of 120-180nm;
Further, the perovskite light-absorption layer is the dimethyl methylamine lead iodine for adulterating potassium rhodanide (KSCN) (MAPbI3), configured perovskite precursor liquid is spin-coated on TiO2It is made on mesoporous layer, is then heated at 100 DEG C 30min, with a thickness of 300-500nm;
Further, the molar percentage that potassium rhodanide is adulterated in perovskite precursor liquid be respectively 0%, 0.5%, 1%, 2%, 3%, wherein doping ratio is best for 1% perovskite battery efficiency highest, lag minimum, stability;
Further, the Spiro-OMeTAD hole transmission layer is the Spiro- containing Li-TFSI and tBP additive OMeTAD chlorobenzene solution is spin-coated on perovskite light-absorption layer, with a thickness of 120-200nm;
Further, the metal electrode be gold or silver, by hot evaporation mode plate on the hole transport layer, with a thickness of 60-100nm。
The preparation method of the perovskite solar battery of doping potassium rhodanide as described above, comprising the following steps:
(1) cleans FTO electro-conductive glass: FTO electro-conductive glass is sequentially placed into detergent solution, deionized water, ethyl alcohol, third In ketone, aqueous isopropanol, each ultrasound 30min or more in ultrasonic machine is then obtained with UV ozone cleaning machine processing 15min clean Net surface;
(2) prepares TiO2Compacted zone: being that raw material prepares TiO using the hydrochloric acid that isopropyl titanate, isopropanol, concentration are 2M2 Then solution spin-coating method is prepared TiO by spin coating solution on FTO2Compacted zone, spin coating parameters are " 3000 turns 30 seconds ", then It is heated 10 minutes at 100 DEG C, finally heats 30 minutes and be slowly cooled to room temperature at 510 DEG C;
(3) prepares TiO2Mesoporous layer: the business titanium slurry that specification is 18-NRT is diluted in ethanol solution, and stirs 10h Uniform sizing material is obtained, then by slurry for rotary coating in TiO2TiO is prepared on compacted zone2Mesoporous layer, spin coating parameters are " 5000 turn 30 Second ", then in 120 DEG C of heating 10min, finally anneals 30 minutes and be slowly cooled to room temperature at 510 DEG C;
(4) configures potassium thiocyanate solution: by potassium rhodanide dissolution of crystals in dimethyl sulfoxide (DMSO) solution, making it Concentration is 1mol/ml;
(5) prepares the perovskite precursor liquid of potassium rhodanide doping: by lead iodide (PbI2), methylamine iodine (MAI) and diformazan Base sulfoxide (DMSO) is dissolved in solution in dimethylformamide (DMF) solution by the molar ratio of 1:1:1, makes their concentration Then solution is stirred 1 hour yellow perovskite precursor liquid for obtaining clear at 40 DEG C by 1.4mol/ml;To not same amount Prepared potassium thiocyanate solution be added in perovskite precursor solution, obtain various concentration potassium rhodanide doping calcium titanium Mine precursor liquid;
(6) prepares perovskite light-absorption layer: calcium titanium ore bed is prepared in glove box using " one-step method ", anti-solvent used is Chlorobenzene, spin coating parameters be 4000 turns 30 seconds, the 100 microlitres of chlorobenzenes of dropwise addition in the 10th second after spin coating starts, at 100 DEG C after spin coating is complete 30min is heated on hot plate;
(7) prepares hole transmission layer: prepared Spiro-OMeTAD solution is spin-coated on calcium with " 3000 turns 30 seconds " parameter On titanium ore layer, after spin coating, entire device is taken out into glove box it is put in drying basin aoxidizing 12 hours;
(8) prepares metal electrode: device being put in vacuum coating equipment, vacuum degree is evacuated to 10-5Then Pa is hereinafter, exist The gold or silver that one layer of 60-100nm thickness is deposited in hole transport layer surface are as to electrode.
Further, TiO is prepared in step (2)2The volume ratio of used isopropyl titanate and hydrochloric acid is when spin coating liquid The volume ratio of 10.5:1, isopropyl titanate and isopropanol is 0.073:1, and solution needs to use after 10-15h is stirred.
Further, TiO is prepared in step (3)2The mass ratio of used titanium slurry and isopropanol is 1:4- when spin coating slurry 1:5.5;The amount for adulterating potassium rhodanide in step (5) in perovskite precursor liquid is molar ratio 0.5%-3%.
The utility model has the advantages that
Compared with common perovskite battery preparation method, present invention be distinguished in that having used potassium rhodanide first It is doped in perovskite precursor liquid, then obtains perovskite light-absorption layer using spin-coating method spin coating perovskite precursor liquid.
The potassium ion being doped in perovskite can be filled into the interstitial site of perovskite crystalline lattice, enhance lattice stability, Internal flaw state is filled, Ion transfer is inhibited;Thiocyanate ion can change crystallization power first with lead iodide ions binding It learns, perovskite crystal grain is promoted to grow up, improve crystalline quality.It is compared through experimental result, the perovskite thin film for adulterating potassium rhodanide is brilliant Grain significantly increases (such as Fig. 2), and defect significantly reduces, and battery efficiency is improved, and hysteresis is suppressed, and stability is increased By force.
Detailed description of the invention
Fig. 1 is the perovskite solar battery structure schematic diagram that potassium rhodanide is adulterated in the present invention.
Fig. 2 is the perovskite thin film scanning electron microscope (SEM) photograph for adulterating 0% (a) and 1% (b) potassium rhodanide, it can be seen that doping 1% The perovskite crystal grain of potassium rhodanide significantly increases.
Fig. 3 is the perovskite thin film stable state photoluminescence spectrum for adulterating 0% and 1% potassium rhodanide, it can be seen that 1% sulphur of doping The perovskite spectrum peak intensity of potassium cyanate obviously becomes larger, and illustrates that internal flaw state significantly reduces.
Fig. 4 is I-V curve figure of the perovskite battery of 0% and 1% potassium rhodanide of doping under AM1.5 illumination, can be seen Perovskite battery efficiency to 1% potassium rhodanide of doping is improved, and lag is obviously reduced.
Specific embodiment
Below in conjunction with the comparative example and embodiment in the present invention, to the technical solution in comparative example of the present invention and embodiment Progress is detailed, is fully described by, but not limited to this.
Comparative example
Step 1: cleaning FTO electro-conductive glass: selecting sheet resistance for 14 Ω, light transmittance 90% is led with a thickness of the FTO of 2.2mm Electric glass is base material, and is successively cleaned in ultrasonic machine using detergent solution, deionized water, ethyl alcohol, acetone, isopropanol It 30 minutes, is then handled 15 minutes with UV ozone cleaning machine, obtains the FTO electro-conductive glass of clean surface.
Step 2: preparing TiO2Precursor liquid simultaneously prepares TiO2Compacted zone: 369 microlitres of isopropyl titanate solution is diluted Into 2.53 milliliters of isopropanols, 35 microlitres of hydrochloric acid solution (concentration 2M) is then diluted to 2.53 milliliters of isopropanol In, finally two kinds of solution are mixed and long agitation obtains TiO2Precursor liquid;By prepared TiO2Precursor liquid exists It is spin-coated on FTO under the parameter of " 3000 turns 30 seconds ", and is heated 10 minutes on 100 DEG C of hot plate, finally in 510 DEG C of high temperature It heats 30 minutes and is cooled to room temperature in furnace.
Step 3: preparation TiO2Mesoporous layer: business titanium slurry (Dyesol 18-NRT) 1:5 in mass ratio is diluted in ethyl alcohol In solution, 10h is stirred, the solution after dilution is then spin-coated on compacted zone TiO with the parameter of " 5000 turns 30 seconds "2On, then 10min is baked on 120 DEG C of hot plates, is finally putting into and is heated 30 minutes and be cooled to room temperature in 510 DEG C of high temperature furnaces.
Step 4: preparing perovskite precursor liquid: by lead iodide (PbI2), methylamine iodine (MAI) and dimethyl sulfoxide (DMSO) by the molar ratio dissolution of 1:1:1 in dimethylformamide (DMF) solution solution, make their concentration 1.4mol/ml, so Solution is stirred into 1 hour yellow perovskite precursor liquid for obtaining clear at 40 DEG C afterwards.
Step 5: the preparation of perovskite light-absorption layer: perovskite light-absorption layer is prepared in glove box using " one-step method ", by calcium Titanium ore precursor liquid drop coating is in mesoporous TiO2On, the spin coating under the parameter of " 4000 turns 30 seconds ", the 10th second after spin coating starts 100 microlitres of chlorobenzene anti-solvent is added dropwise, device is transferred on 100 DEG C of hot plate after spin coating and heats 30 minutes formation calcium titaniums Mine phase.
Step 6: preparing Spiro-OMeTAD solution: the Spiro-OMeTAD of 72.3mg being dissolved in 1ml chlorobenzene, then 17.5 microlitres of Li-TFSI solution (520mgLi-TFSI is dissolved in 1ml acetonitrile) is added, adds 29 microlitres of 4- tert-butyl pyrrole The very bell faint yellow Spiro-OMeTAD solution at clear is stirred at room temperature in pyridine (tBP).
Step 7: preparing hole transmission layer: after the perovskite heating in step 5 is finished and is cooled to room temperature, in glove box It is middle to be spin-coated on prepared Spiro-OMeTAD solution on calcium titanium ore bed with " 3000 turns 30 seconds " parameter, it, will after spin coating Entire device, which is taken out glove box and is put in drying basin, to be aoxidized 12 hours.
Step 8: preparing metal electrode: the device for executing the step one to seven is put in thermal evaporation vacuum coating equipment, it will Vacuum degree is evacuated to 10-5Then Pa in the metallic silver of one layer of 60-100nm thickness of hole transmission layer surface evaporation hereinafter, be used as to electrode.
Embodiment 1
Step 1: cleaning FTO electro-conductive glass: selecting sheet resistance for 14 Ω, light transmittance 90% is led with a thickness of the FTO of 2.2mm Electric glass is base material, and is successively cleaned in ultrasonic machine using detergent solution, deionized water, ethyl alcohol, acetone, isopropanol It 30 minutes, is then handled 15 minutes with UV ozone cleaning machine, obtains the FTO electro-conductive glass of clean surface.
Step 2: preparing TiO2Precursor liquid simultaneously prepares TiO2Compacted zone: 369 microlitres of isopropyl titanate solution is diluted Into 2.53 milliliters of isopropanols, 35 microlitres of hydrochloric acid solution (concentration 2M) is then diluted to 2.53 milliliters of isopropanol In, finally two kinds of solution are mixed and long agitation obtains TiO2Precursor liquid;By prepared TiO2Precursor liquid exists It is spin-coated on FTO under the parameter of " 3000 turns 30 seconds ", and is heated 10 minutes on 100 DEG C of hot plate, finally in 510 DEG C of high temperature It heats 30 minutes and is cooled to room temperature in furnace.
Step 3: preparation TiO2Mesoporous layer: business titanium slurry (Dyesol 18-NRT) 1:5 in mass ratio is diluted in ethyl alcohol In solution, 10h is stirred, the solution after dilution is then spin-coated on compacted zone TiO with the parameter of " 5000 turns 30 seconds "2On, then 10min is baked on 120 DEG C of hot plates, is finally putting into and is heated 30 minutes and be cooled to room temperature in 510 DEG C of high temperature furnaces.
Step 4: preparing potassium thiocyanate solution: by potassium rhodanide dissolution of crystals in dimethyl sulfoxide (DMSO) solution, making Its concentration is 1mol/ml;
Step 5: preparing the perovskite precursor liquid of potassium rhodanide doping: by lead iodide (PbI2), methylamine iodine (MAI) and Dimethyl sulfoxide (DMSO) is dissolved in solution in dimethylformamide (DMF) solution by the molar ratio of 1:1:1, makes their concentration Then solution is stirred 1 hour yellow perovskite precursor liquid for obtaining clear at 40 DEG C by 1.4mol/ml.7 microlitres are taken to match The potassium thiocyanate solution made is added in the perovskite precursor solution of 1ml, obtains the doping of 0.5% (molar ratio) potassium rhodanide Perovskite precursor liquid.
Step 6: the preparation of perovskite light-absorption layer: perovskite light-absorption layer is prepared in glove box using " one-step method ", by sulphur The perovskite precursor liquid drop coating of potassium cyanate doping is in mesoporous TiO2On, the spin coating under the parameter of " 4000 turns 30 seconds ", in spin coating Device, is transferred on 100 DEG C of hot plate after spin coating and heats by the chlorobenzene anti-solvent for being added dropwise 100 microlitres on the 10th second after beginning 30 minutes formation Perovskite Phases.
Step 7: preparing Spiro-OMeTAD solution: the Spiro-OMeTAD of 72.3mg being dissolved in 1ml chlorobenzene, then 17.5 microlitres of Li-TFSI solution (520mgLi-TFSI is dissolved in 1ml acetonitrile) is added, adds 29 microlitres of 4- tert-butyl pyrrole The very bell faint yellow Spiro-OMeTAD solution at clear is stirred at room temperature in pyridine (tBP).
Step 8: preparing hole transmission layer: after the perovskite heating in step 5 is finished and is cooled to room temperature, in glove box It is middle to be spin-coated on prepared Spiro-OMeTAD solution on calcium titanium ore bed with " 3000 turns 30 seconds " parameter, it, will after spin coating Entire device, which is taken out glove box and is put in drying basin, to be aoxidized 12 hours.
Step 9: preparing metal electrode: the device for executing the step one to seven is put in thermal evaporation vacuum coating equipment, it will Vacuum degree is evacuated to 10-5Then Pa in the metallic silver of one layer of 60-100nm thickness of hole transmission layer surface evaporation hereinafter, be used as to electrode.
Embodiment 2
Step 1: cleaning FTO electro-conductive glass: with step 1 in embodiment 1.
Step 2: preparing TiO2Precursor liquid simultaneously prepares TiO2Compacted zone: with step 2 in embodiment 1.
Step 3: preparation TiO2Mesoporous layer: with step 3 in embodiment 1.
Step 4: preparing potassium thiocyanate solution: with step 4 in embodiment 1.
Step 5: preparing the perovskite precursor liquid of potassium rhodanide doping: by lead iodide (PbI2), methylamine iodine (MAI) and Dimethyl sulfoxide (DMSO) is dissolved in solution in dimethylformamide (DMF) solution by the molar ratio of 1:1:1, makes their concentration Then solution is stirred 1 hour yellow perovskite precursor liquid for obtaining clear at 40 DEG C by 1.4mol/ml.Take 14 microlitres Prepared potassium thiocyanate solution is added in the perovskite precursor solution of 1ml, obtains the doping of 1% (molar ratio) potassium rhodanide Perovskite precursor liquid.
Step 6: the preparation of perovskite light-absorption layer: with step 6 in embodiment 1.
Step 7: preparing Spiro-OMeTAD solution: with step 7 in embodiment 1.
Step 8: preparing hole transmission layer: with step 8 in embodiment 1.
Step 9: preparing metal electrode: with step 9 in embodiment 1.
Embodiment 3
Step 1: cleaning FTO electro-conductive glass: with step 1 in embodiment 1.
Step 2: preparing TiO2Precursor liquid simultaneously prepares TiO2Compacted zone: with step 2 in embodiment 1.
Step 3: preparation TiO2Mesoporous layer: with step 3 in embodiment 1.
Step 4: preparing potassium thiocyanate solution: with step 4 in embodiment 1.
Step 5: preparing the perovskite precursor liquid of potassium rhodanide doping: by lead iodide (PbI2), methylamine iodine (MAI) and Dimethyl sulfoxide (DMSO) is dissolved in solution in dimethylformamide (DMF) solution by the molar ratio of 1:1:1, makes their concentration Then solution is stirred 1 hour yellow perovskite precursor liquid for obtaining clear at 40 DEG C by 1.4mol/ml.Take 28 microlitres Prepared potassium thiocyanate solution is added in the perovskite precursor solution of 1ml, obtains the doping of 2% (molar ratio) potassium rhodanide Perovskite precursor liquid.
Step 6: the preparation of perovskite light-absorption layer: with step 6 in embodiment 1.
Step 7: preparing Spiro-OMeTAD solution: with step 7 in embodiment 1.
Step 8: preparing hole transmission layer: with step 8 in embodiment 1.
Step 9: preparing metal electrode: with step 9 in embodiment 1.
Embodiment 4
Step 1: cleaning FTO electro-conductive glass: with step 1 in embodiment 1.
Step 2: preparing TiO2Precursor liquid simultaneously prepares TiO2Compacted zone: with step 2 in embodiment 1.
Step 3: preparation TiO2Mesoporous layer: with step 3 in embodiment 1.
Step 4: preparing potassium thiocyanate solution: with step 4 in embodiment 1.
Step 5: preparing the perovskite precursor liquid of potassium rhodanide doping: by lead iodide (PbI2), methylamine iodine (MAI) and Dimethyl sulfoxide (DMSO) is dissolved in solution in dimethylformamide (DMF) solution by the molar ratio of 1:1:1, makes their concentration Then solution is stirred 1 hour yellow perovskite precursor liquid for obtaining clear at 40 DEG C by 1.4mol/ml.Take 42 microlitres Prepared potassium thiocyanate solution is added in the perovskite precursor solution of 1ml, obtains the doping of 3% (molar ratio) potassium rhodanide Perovskite precursor liquid.
Step 6: the preparation of perovskite light-absorption layer: with step 6 in embodiment 1.
Step 7: preparing Spiro-OMeTAD solution: with step 7 in embodiment 1.
Step 8: preparing hole transmission layer: with step 8 in embodiment 1.
Step 9: preparing metal electrode: with step 9 in embodiment 1.
Performance test
Stable state luminescence generated by light spectral characterization (Fig. 3) is done to perovskite thin film, to perovskite battery in a standard sun light intensity Under do photovoltaic performance test (Fig. 4).
Technical solution of the present invention and beneficial effect is described in detail in particular embodiments described above, is answered Understand, the above is only a specific embodiment of the present invention, is not intended to restrict the invention, all in spirit of that invention Within principle, any modification, equivalent substitution, improvement and etc. done be should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of perovskite solar battery for adulterating potassium rhodanide, it is characterised in that: the battery is respectively FTO from bottom to top Conductive glass layer, compact titanium dioxide layer, meso-porous titanium dioxide titanium layer, perovskite absorbed layer, hole transmission layer and metal electrode.
2. a kind of perovskite solar battery for adulterating potassium rhodanide as described in claim 1, it is characterised in that: described The sheet resistance of FTO electro-conductive glass be 14 Ω, light transmittance 90%, FTO electro-conductive glass with a thickness of 2.2 millimeters.
3. a kind of perovskite solar battery for adulterating potassium rhodanide as described in claim 1, it is characterised in that: the cause For close titanium dioxide layer with a thickness of 50-100nm, the used raw material for preparing is isopropyl titanate.
4. a kind of perovskite solar battery for adulterating potassium rhodanide as described in claim 1, it is characterised in that: Jie For porous titanium dioxide layer with a thickness of 100-200nm, used titanium dioxide specification is 18-NRT.
5. a kind of perovskite solar battery for adulterating potassium rhodanide as described in claim 1, it is characterised in that: the calcium Titanium ore light-absorption layer contains dimethyl methylamine iodine (MAI) and lead iodide (PbI with a thickness of 300-600nm, interior remove of calcium titanium ore bed2) outside, The potassium rhodanide for being also 0.5%-3% doped with molar ratio, the performance of the perovskite battery obtained when doping is 1% is most It is good.
6. a kind of perovskite solar battery for adulterating potassium rhodanide as described in claim 1, it is characterised in that: the sky For cave transport layer with a thickness of 100-200nm, used material is Spiro-OMeTAD (2,2', 7,7'- tetra- [(the 4- methoxies of N, N- bis- Base phenyl) amino] two fluorenes of -9,9'- spiral shell).
7. a kind of perovskite solar battery for adulterating potassium rhodanide as described in claim 1, it is characterised in that: the gold Belonging to electrode is gold or silver, with a thickness of 60-100nm.
8. a kind of preparation method for the perovskite solar battery for adulterating potassium rhodanide, it is characterised in that the following steps are included:
(1) cleans FTO electro-conductive glass: FTO electro-conductive glass is sequentially placed into detergent solution, deionized water, ethyl alcohol, acetone, different In propanol solution, each ultrasound 30min or more in ultrasonic machine then obtains clean table with UV ozone cleaning machine processing 15min Face;
(2) prepares TiO2Compacted zone: being that raw material prepares TiO using the hydrochloric acid that isopropyl titanate, isopropanol, concentration are 2M2Spin coating Then solution spin-coating method is prepared TiO by solution on FTO2Compacted zone, spin coating parameters are " 3000 turns 30 seconds ", then 100 DEG C heating 10 minutes, finally heat 30 minutes and be slowly cooled to room temperature at 510 DEG C;
(3) prepares TiO2Mesoporous layer: the business titanium slurry that specification is 18-NRT is diluted in ethanol solution, and stirs 10h acquisition Uniform sizing material, then by slurry for rotary coating in TiO2TiO is prepared on compacted zone2Mesoporous layer, spin coating parameters are " 5000 turns 30 seconds ", Then it in 120 DEG C of heating 10min, finally anneals 30 minutes and is slowly cooled to room temperature at 510 DEG C;
(4) configures potassium thiocyanate solution: by potassium rhodanide dissolution of crystals in dimethyl sulfoxide (DMSO) solution, making its concentration For 1mol/ml;
(5) prepares the perovskite precursor liquid of potassium rhodanide doping: by lead iodide (PbI2), methylamine iodine (MAI) and dimethyl it is sub- Sulfone (DMSO) is dissolved in solution in dimethylformamide (DMF) solution by the molar ratio of 1:1:1, makes their concentration 1.4mol/ml, Then solution is stirred into 1 hour yellow perovskite precursor liquid for obtaining clear at 40 DEG C;It will be different amounts of prepared Potassium thiocyanate solution is added in perovskite precursor solution, obtains the perovskite presoma of various concentration potassium rhodanide doping Liquid;
(6) prepares perovskite light-absorption layer: calcium titanium ore bed is prepared in glove box using " one-step method ", anti-solvent used is chlorobenzene, Spin coating parameters be 4000 turns 30 seconds, the 100 microlitres of chlorobenzenes of dropwise addition in the 10th second after spin coating starts, in 100 DEG C of hot plates after spin coating is complete Upper heating 30min;
(7) prepares hole transmission layer: prepared Spiro-OMeTAD solution is spin-coated on perovskite with " 3000 turns 30 seconds " parameter On layer, after spin coating, entire device is taken out into glove box it is put in drying basin aoxidizing 12 hours;
(8) prepares metal electrode: device being put in vacuum coating equipment, vacuum degree is evacuated to 10-5Pa is hereinafter, then in hole Transmit the gold or silver-colored as to electrode that one layer of 60-100nm thickness is deposited in layer surface.
9. a kind of preparation method of perovskite solar battery for adulterating potassium rhodanide as claimed in claim 8, feature exist In: TiO is prepared in step (2)2The volume ratio of used isopropyl titanate and hydrochloric acid is 10.5:1, isopropyl titanate when spin coating liquid Volume ratio with isopropanol is 0.073:1, and solution needs to use after 10-15h is stirred.
10. a kind of preparation method of perovskite solar battery for adulterating potassium rhodanide as claimed in claim 8, feature exist In: TiO is prepared in step (3)2The mass ratio of used titanium slurry and isopropanol is 1:4-1:5.5 when spin coating slurry;In step (5) The amount that potassium rhodanide is adulterated in perovskite precursor liquid is molar ratio 0.5%-3%.
CN201810988707.6A 2018-08-28 2018-08-28 A kind of perovskite solar battery and preparation method thereof adulterating potassium rhodanide Pending CN109244251A (en)

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