CN106784338A - A kind of Ca-Ti ore type opto-electronic conversion composite sol and preparation method thereof - Google Patents

A kind of Ca-Ti ore type opto-electronic conversion composite sol and preparation method thereof Download PDF

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Publication number
CN106784338A
CN106784338A CN201611021883.XA CN201611021883A CN106784338A CN 106784338 A CN106784338 A CN 106784338A CN 201611021883 A CN201611021883 A CN 201611021883A CN 106784338 A CN106784338 A CN 106784338A
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pbx
ore type
electronic conversion
sol
opto
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李建生
胡兴兰
王韬
刘炳光
崔明月
凌小芳
王璐瑶
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Tianjin Vocational Institute
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • 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
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Abstract

The present invention relates to a kind of Ca-Ti ore type opto-electronic conversion composite sol and preparation method thereof, Ca-Ti ore type opto-electronic conversion composite sol is mixed with using imidodicarbonic diamide and methylamine with photosensitive activity, the band gap and filming performance of Ca-Ti ore type light absorbing material is adjusted.Ca-Ti ore type opto-electronic conversion composite sol of the present invention is made up of lead halide, imidodicarbonic diamide halogen acid salt, methylamine halogen acid salt, dehydration catalyst, nano-oxide and organic solvent.The opto-electronic conversion composite material film to be formed is coated with using composite sol of the present invention has more preferable electronics or holoe carrier transmission performance, the light absorption wavelength scope that can extend sunshine and the photoelectric transformation efficiency 1.5% 2% for improving perovskite solar cell.

Description

A kind of Ca-Ti ore type opto-electronic conversion composite sol and preparation method thereof
Technical field
The present invention relates to a kind of Ca-Ti ore type opto-electronic conversion composite sol and preparation method thereof, especially with two acyls Imines and methylamine are mixed with Ca-Ti ore type opto-electronic conversion composite sol, with adjust Ca-Ti ore type light absorbing material band gap and Photoelectric transformation efficiency is improved, belongs to new energy and field of new.
Technical background
The solar cell prepared based on organic metal halide perovskite structure light absorbing material is referred to as perovskite too Positive electricity pond, more than 20%, future is expected to reach 50% current its photoelectric transformation efficiency.Perovskite solar cell is typically by saturating Bright electro-conductive glass, compacted zone, perovskite light absorbing zone, hole transmission layer, the part of metal back electrode five composition.Perovskite light absorbs The thickness of layer is generally 200-600nm, and Main Function is to absorb sunshine and produce electron-hole pair, and can high efficiency of transmission electricity Son-hole pair.
Perovskite light absorbing material Typical molecular formula is AMX3, wherein, A represents the ammonium ion or metal ion of monovalence, M Metal cation is represented, X represents halide anion.Research both at home and abroad to metal cation and halide anion at present is compared Thoroughly, composition but to the ammonium ion of monovalence, structurally and functionally Mechanism Study is little and unclear.
At present both at home and abroad to Ca-Ti ore type light absorbing material iodate methylamine lead（CH3NH3PbI3）Research it is relatively more, it be by Iodine methylamine and a kind of inorganic-organic double salt or complex of lead iodide reaction generation, it is also a kind of Semiconductor absorption Material, its band gap is about 1.5eV, can fully absorb the visible ray of wavelength 400-800nm, with absorbing properties are good, system Standby simple and photoelectric transformation efficiency characteristic high.Its main deficiency is：（1）Temperature tolerance is bad, it is desirable to the heat treatment of light absorbing zone Temperature is less than 150 DEG C, and the additive during at such a temperature prepared by light absorbing zone can not be decomposed completely；（2）Environmental stability is poor, It is easily moisture, ultraviolet light or catalyst decomposition in air；（3）Absorb optical wavelength range and be confined to visible region, to ultraviolet light Hardly picked up with infrared light；（4）Filming performance is bad, easily forms loose thick crystalline solid, it is difficult to which large area is uniformly applied Cloth.
Improve Ca-Ti ore type light absorbing material performance, can start with from the composition design of Ca-Ti ore type light absorbing material.For example, The biological institute in Chinese Academy of Sciences Qingdao prepares perovskite structure light absorbing material using the primary amine of C1-C4, carbonamidine or its mixture, and acquisition is good Good photoelectric transformation efficiency；Xiamen University's patent of invention CN106058060 (2016-10-25) is open mixed using methylamine and carbonamidine Conjunction prepares perovskite structure light absorbing material film；Wuhan University of Technology's patent of invention CN105742502 (2016-07-06) is public Exploitation iodobenzene ethamine, stannous iodide and lead iodide are mixed with the adjustable perovskite structure light absorbing material of band gap；Central China section Skill university patent of invention CN103762344 (2014-04-30) is open to be mixed with calcium using aminobutyric acid amphiphatic molecule and methylamine Perovskite like structure light absorbing material；United States Patent (USP) US20150249170 (2015-09-03) disclosure long-chain organic amine prepares calcium titanium Ore deposit structure light absorbing material, but without the details of open long-chain organic amine；United States Patent (USP) US20150200377 (2015- 07-16) open a series of primary, secondary, uncles, quaternary ammonium compound prepare perovskite structure light absorbing material, but without offer amine The embodiment of compound；Chinese patent CN103554171 (2014-02-05) is open to use 1- aminopyridines azomethine and chlorination Lead coordinates as potential dielectric material；The open 1- ethyl-3-methylimidazoles of Chinese patent CN102337593 (2012-02-01) Tribromide iodine perovskite structure light absorbing material preparation method.
Improve perovskite light absorping film performance, it is also possible to start with from perovskite light absorbing material structure.For example, Singapore is southern Foreign Polytechnics's patent of invention WO2016126211 (2016-08-11) is disclosed perovskite light absorbing material and nanoclay grain Son forms colloidal sol in organic solvent, nano-particle as crystal seed, improve perovskite light absorbing material microstructure and into Film properties；Tianjin Professional College patent of invention CN105789339 (2016-07-20) it is open by perovskite light absorbing material with Nano-silicon dioxide particle forms colloidal sol in organic solvent, and nano-particle is used as light absorbing material crystal seed and framework material, one Step obtains the light absorbing zone of smooth even；Nankai University's patent of invention CN104218109 (2014-12-17) is open by polyethylene Pyrrolidones mixes with perovskite light absorbing material, improves the microstructure and filming performance of perovskite light absorbing material, greatly It is big to improve photoelectric transformation efficiency.
Although perovskite photoelectric conversion efficiency of the solar battery data constantly refresh, from Ca-Ti ore type light in terms of research angle Organic cation less varieties and potential of innovation are big in absorbing material；From perovskite light absorbing material filming performance in terms of application angle Difference, is not met by the engineering coating of large area perovskite solar cell light absorption layer and requires.Heliotechnics is developed and industry The three big key elements changed are photoelectric transformation efficiency, production cost and battery performance stability, and market needs photoelectric transformation efficiency Perovskite solar cell photoelectric conversion material higher.
The content of the invention
It is an object of the invention to provide a kind of Ca-Ti ore type opto-electronic conversion composite sol, from perovskite light absorbing material Composition and the aspect of microstructure two are started with and improve its filming performance, to adapt to the preparation of large area perovskite solar cell light absorption layer Need.
The present invention is mixed with Ca-Ti ore type opto-electronic conversion composite wood using imidodicarbonic diamide and methylamine with photosensitive activity Material colloidal sol, adjusts Ca-Ti ore type light absorbing material band gap and filming performance, and composite sol is by lead halide（PbX2）, two acyls it is sub- Amine halogen acid salt（RC2O2NH2X）, methylamine halogen acid salt（CH3NH3X）, dehydration catalyst, nano-oxide and organic solvent group Into each component mol ratio is as follows in colloidal sol：
PbX2 1
RC2O2NH2X x, x=0.1-0.9
CH3NH3X 1-x
Nano-oxide 0.01-0.05
Dehydration catalyst 0.01-0.05
Organic solvent 20-60.
PbX in the present invention2It is to form Ca-Ti ore type opto-electronic conversion composite RC2O2NH2PbX3And CH3NH3PbX3Original Material, is commercially available chemical reagent.
Heretofore described imidodicarbonic diamide is succimide, butylmaleimide, glutarimide, phthalyl Asia One of amine, tetrahydric phthalimide, hexahydrophthalic phthalimide or naphthalimide, are commercially available chemical reagent.Two The compound of imide structure is organic photosensitive material and photoelectron acceptor, and the salt of stabilization, energy can be generated with halogen acids reaction Enough and metal ion forms ligand or complex compound, so novel inorganic-organic hybrid further can be generated with lead halide reaction Ca-Ti ore type photoelectric conversion material, and with broader sunlight wavelength absorption region.
Methylamine halogen acid salt is that methylamine reacts generation with halogen acids in colloidal sol of the present invention；Imidodicarbonic diamide halogen acid salt is two Acid imide and halogen acids reaction generation.
Dehydration catalyst is one of magnesium methoxide, magnesium ethylate, triethyl aluminum or aluminum alkoxide in the present invention, is commercially available chemistry examination Agent.For maintaining colloidal sol in alkalescent, imidodicarbonic diamide halogen acid salt is promoted to be formed with halogenation lead source, while de- as solvent Water catalyst and generation magnesia or alumina nanoparticles.
Nano-oxide is that dehydration catalyst is generated with reaction of moisture in solution in the basic conditions in colloidal sol of the present invention Nano-particle, can as Ca-Ti ore type photoelectric conversion material film forming when nucleus, change material microstructure, prevent photoelectricity turn Conversion materials form thick crystallization.
Organic solvent is the mixed of dimethylformamide, gamma-butyrolacton or dimethyl sulfoxide (DMSO) and C1-C4 fatty alcohols in the present invention Compound.Dimethylformamide, gamma-butyrolacton or dimethyl sulfoxide (DMSO) polar solvent are used to dissolve PbX2、CH3NH3PbX3With RC2O2NH2PbX3, C1-C4 fatty alcohols, as retarder thinner, are commercially available chemical reagent.
There is halogenation lead molecule, methylamine halogen acid salt molecule and imidodicarbonic diamide halogen acid salt molecule in colloidal sol of the present invention, with And a small amount of RC with nanometer oxide particle as nucleus2O2NH2PbX3And CH3NH3PbX3Micelle or crystal seed, when solvent volatilizees, Under coordination, hydrogen bond, the common driving of Van der Waals force, halogenation lead molecule, molecule imidodicarbonic diamide halogen acid salt molecule and first Amine halogen acid salt is self-assembly of Ca-Ti ore type opto-electronic conversion composite material film on crystal seed.
Imidodicarbonic diamide in the present invention is a kind of photosensitive organic dye groups cheap and easy to get, is had very in visible region Strong light absorbs, and with light and thermally stable higher.Imidodicarbonic diamide molecule has annular carbonyl structure, and carbonyl is connected with One NH key, this enables imidodicarbonic diamide as weak acid, anion and metal-complexing is formed under alkaline environment.With solution The increase of alkalescence, the complex that imidodicarbonic diamide is formed with metal ion gradually changes to more stable co-ordination state.If using Imidodicarbonic diamide prepares new Ca-Ti ore type photoelectric conversion material RC instead of methylamine2O2NH2PbX3, will be with more preferable electronics or sky Cave carrier transmission performance, can reduce the dimensional effect of large area perovskite solar cell, can extend the light to sunshine Absorbing wavelength scope and raising photoelectric transformation efficiency.
It is a further object of the present invention to provide a kind of preparation method of Ca-Ti ore type opto-electronic conversion composite sol, prepare Technical scheme is comprised the following steps：
（1）Polar organic solvent, HX and PbX are separately added into glass reactor2, stirred at 60-80 DEG C to being completely dissolved, Imide compound is subsequently adding, controls the raw material molar ratio to be：PbX2：HX：Imidodicarbonic diamide=1：1：X, wherein, x =0.1-0.9, continues stirring reaction 12-24 h, obtains RC2O2NH2PbX3Solution；
（2）To the methanol solution that methylamine is added in above reaction solution, the raw material molar ratio is controlled to be：PbX2：HX：Methylamine= 1：1：1-x, continues stirring reaction 12-24h, is cooled to room temperature, obtains RC2O2NH2PbX3And CH3NH3PbX3Mixed solution；
（3）To dehydration catalyst is added in above reaction solution, the raw material molar ratio is controlled to be：PbX2：Dehydration catalyst=1： 0.02-0.1, dehydration catalyst forms nanometer oxide particle colloidal sol with the reaction of moisture 1-4h in solution, and particle diameter is 5-10nm；
（4）To addition C1-C4 fatty alcohols in above reaction solution to PbX2Saturation is separated out, and becomes cloudy colloidal sol, then in 90-100 Flow back 12-24 h at DEG C, and generation contains RC2O2NH2PbX3And CH3NH3PbX3The colloidal sol of crystal seed, the quality percentage of solid in colloidal sol Concentration is 10%-20%；
（5）With biscuit ware funnel secondary filter composite sol, with dropper by colloidal sol drop in the 200mm of compacted zone × In 300mm fluorine-doped tin dioxide Conducting Glass, it is coated with uniformly with stainless steel wire rod coating device, solvent is volatilized and dry, most 110-150 DEG C of heated-air drying 30 minutes, forms the smooth black Ca-Ti ore type light absorbing zone in surface, assembling test perovskite afterwards Solar cell, using RC2O2NH2PbX3And CH3NH3PbX3Composite than uses CH merely3NH3PbX3Opto-electronic conversion during material Efficiency improves 1.5%-2%.
The absorbing properties of the photoelectric conversion material film type spectrophotometer test specimens of Lambda 920 in the present invention Absorptivity of the product in 250-1100nm wave-length coverages determines；Test is special with reference to Chinese invention with the assembling of perovskite solar cell Profit application 2019109316795（2016-10-25）The method of middle use is carried out；Efficiency of solar cell using customization it is small-sized too Positive electricity pond component tester simulated solar optical tests.
Beneficial effects of the present invention are embodied in：
（1）The present invention improves its filming performance in terms of perovskite photoelectric conversion material composition and microstructure two, adapts to big face Product perovskite solar cell light absorption layer is prepared and needed；
（2）The present invention prepares new perovskite photoelectric conversion material with the imidodicarbonic diamide with photosensitive activity, with more preferable electricity Son or holoe carrier transmission performance, can reduce the dimensional effect of large area perovskite thin film solar cell；
（3）The present invention is mixed with Ca-Ti ore type photoelectric conversion material with imidodicarbonic diamide and methylamine, can extend to sunshine Light absorption wavelength scope and raising photoelectric transformation efficiency 1.5%-2%.
Specific embodiment
Embodiment 1
Dimethylformamide 365.5g (5mol), mass percentage concentration are separately added into the 500mL glass reactors of band stirring 50% hydroiodic acid 30.7g (0.12mol) and lead iodide 46.1g (0.1mol), stirs 2h to being completely dissolved at 60-80 DEG C, Succimide 4.96g (0.05mol) is subsequently adding, continues the h of stirring reaction 24, obtain C4H4O2NH2PbI3Solution；Add The methanol solution 5.18g (0.05mol) of the methylamine of mass percentage concentration 30%, continues the h of stirring reaction 12, is cooled to room temperature, obtains To C4H4O2NH2PbI3And CH3NH3PbI3Mixed light absorbent solution.
To methyl alcohol magnesium solution 29.2g (0.05mol) that addition mass percentage concentration in above reaction solution is 20%, magnesium methoxide Bitter earth nano colloidal sol is formed with reaction of moisture 4h, particle diameter is 5nm.Continuously add absolute ethyl alcohol to PbI2Saturation is separated out, Colloidal sol is set to be in slightly cloudy, then flow back 24 h at 90-100 DEG C, generation contains C4H4O2NH2PbI3And CH3NH3PbI3Crystal seed Colloidal sol.With G5 biscuit ware funnel secondary filter light absorbing material colloidal sols, with dropper by colloidal sol drop in the 200mm of compacted zone × In 300mm fluorine-doped tin dioxide Conducting Glass, it is coated with uniformly with stainless steel wire rod coating device, solvent is volatilized and dry, most 110-150 DEG C of heated-air drying 30 minutes, forms the smooth black perovskite light absorbing zone in surface, as assembling test calcium titanium afterwards Ore deposit solar cell, than using simple CH3NH3PbX3Photoelectric transformation efficiency improves 1.5% during material.
Embodiment 2
Dimethylformamide 365.5g (5mol), mass percentage concentration are separately added into the 500mL glass reactors of band stirring 50% hydroiodic acid 30.7g (0.12mol) and lead iodide 46.1g (0.1mol), stirs 2h to being completely dissolved at 60-80 DEG C, Phthalimide 2.94g (0.02mol) is subsequently adding, continues the h of stirring reaction 24, obtain C8H4O2NH2PbI3Solution；Again The methanol solution 8.288g (0.08mol) of the methylamine of mass percentage concentration 30% is added, continues the h of stirring reaction 12, be cooled to room Temperature, obtains C8H4O2NH2PbI3And CH3NH3PbI3Mixed light absorbent solution.
To aluminium isopropoxide solution 20.4g (0.02mol) that addition mass percentage concentration in above reaction solution is 20%, isopropyl Aluminium alcoholates forms nano alumina particles colloidal sol with reaction of moisture 4h in solution, and particle diameter is 10nm.Continuously add absolute ethyl alcohol extremely PbI2Saturation is separated out, and makes colloidal sol be in slightly cloudy, and then flow back 24 h at 90-100 DEG C, and generation contains C8H4O2NH2PbI3With CH3NH3PbI3The colloidal sol of crystal seed.With G5 biscuit ware funnel secondary filter light absorbing material colloidal sols, colloidal sol is dropped in dropper In 200mm × 300mm fluorine-doped tin dioxide Conducting Glass of compacted zone, it is coated with uniformly with stainless steel wire rod coating device, is made Solvent volatilization is dried, last 110-150 DEG C of heated-air drying 30 minutes, forms the smooth black perovskite light absorbing zone in surface, is used Make assembling test perovskite solar cell, than using simple CH3NH3PbX3Photoelectric transformation efficiency improves 2.0% during material.

Claims (4)

1. a kind of Ca-Ti ore type opto-electronic conversion composite sol, it is characterized in that using imidodicarbonic diamide and first with photosensitive activity Amine mix with lead halide reaction prepare Ca-Ti ore type opto-electronic conversion composite, with adjust Ca-Ti ore type light absorbing material band gap and Filming performance, composite sol is by lead halide, imidodicarbonic diamide halogen acid salt, methylamine halogen acid salt, dehydration catalyst, nano oxygen Compound and organic solvent are constituted, and each component mol ratio is as follows in colloidal sol：
PbX2 1
RC2O2NH2X x, x=0.1-0.9
CH3NH3X 1-x
Nano-oxide 0.01-0.05
Dehydration catalyst 0.01-0.05
Organic solvent 20-60.
2. Ca-Ti ore type opto-electronic conversion composite sol as claimed in claim 1, it is characterised in that imidodicarbonic diamide is succinyl Imines, butylmaleimide, glutarimide, phthalimide, tetrahydric phthalimide, hexahydro phthalyl One of imines or naphthalimide.
3. Ca-Ti ore type opto-electronic conversion composite sol as claimed in claim 1, it is characterised in that dehydration catalyst is methyl alcohol One of magnesium, magnesium ethylate, triethyl aluminum or aluminum alkoxide.
4. the preparation method of Ca-Ti ore type opto-electronic conversion composite sol described in a kind of claim 1, it is characterised in that prepare Technical scheme is comprised the following steps：
（1）Polar organic solvent, HX and PbX are separately added into glass reactor2, stir completely molten to solid at 60-80 DEG C Solution, imide compound is subsequently adding, control the raw material molar ratio to be：PbX2：HX：Imidodicarbonic diamide=1:1:X, its In, x=0.1-0.9 continue stirring reaction 12-24 h, obtain RC2O2NH2PbX3Solution；
（2）To the methanol solution that methylamine is added in above reaction solution, the raw material molar ratio is controlled to be：PbX2：HX：Methylamine= 1:1:1-x, continues stirring reaction 12-24 h, is cooled to room temperature, obtains RC2O2NH2PbX3And CH3NH3PbX3Mixed solution；
（3）To dehydration catalyst is added in above reaction solution, the raw material molar ratio is controlled to be：PbX2：Dehydration catalyst=1: 0.02-0.1, dehydration catalyst forms nanometer oxide particle colloidal sol with the reaction of moisture 1-4h in solution, and particle diameter is 5-10nm；
（4）To addition C1-C4 fatty alcohols in above reaction solution to PbX2Saturation is separated out, and becomes cloudy colloidal sol, then at 90-100 DEG C Lower backflow 12-24 h, generation contains RC2O2NH2PbX3And CH3NH3PbX3The colloidal sol of crystal seed, the quality percentage of solid is dense in colloidal sol It is 10%-20% to spend；
（5）With biscuit ware funnel secondary filter composite sol, with dropper by colloidal sol drop in the 200mm of compacted zone × In 300mm fluorine-doped tin dioxide Conducting Glass, it is coated with uniformly with stainless steel wire rod coating device, solvent is volatilized and dry, most 110-150 DEG C of heated-air drying 30 minutes, forms the smooth black Ca-Ti ore type light absorbing zone in surface, assembling test perovskite afterwards Solar cell, using RC2O2NH2PbX3And CH3NH3PbX3Composite than uses CH merely3NH3PbX3Opto-electronic conversion during material Efficiency improves 1.5%-2%.
CN201611021883.XA 2016-11-21 2016-11-21 A kind of Ca-Ti ore type opto-electronic conversion composite sol and preparation method thereof Pending CN106784338A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107442182A (en) * 2017-08-16 2017-12-08 天津市职业大学 A kind of photoelectrocatalysis gray haze removes coating and preparation method thereof
CN116003819A (en) * 2023-02-03 2023-04-25 国科大杭州高等研究院 Covalent organic framework material containing imine bond and metal halide perovskite composite material, and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN105489765A (en) * 2015-12-22 2016-04-13 成都新柯力化工科技有限公司 Water-resistant perovskite photovoltaic material and preparation method therefor
CN105514277A (en) * 2015-12-21 2016-04-20 成都新柯力化工科技有限公司 Wide-range spectral absorption perovskite photovoltaic material and preparation method thereof
CN106450002A (en) * 2016-11-14 2017-02-22 天津市职业大学 Perovskite type photovoltaic-conversion composite sol and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN105514277A (en) * 2015-12-21 2016-04-20 成都新柯力化工科技有限公司 Wide-range spectral absorption perovskite photovoltaic material and preparation method thereof
CN105489765A (en) * 2015-12-22 2016-04-13 成都新柯力化工科技有限公司 Water-resistant perovskite photovoltaic material and preparation method therefor
CN106450002A (en) * 2016-11-14 2017-02-22 天津市职业大学 Perovskite type photovoltaic-conversion composite sol and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107442182A (en) * 2017-08-16 2017-12-08 天津市职业大学 A kind of photoelectrocatalysis gray haze removes coating and preparation method thereof
CN116003819A (en) * 2023-02-03 2023-04-25 国科大杭州高等研究院 Covalent organic framework material containing imine bond and metal halide perovskite composite material, and preparation method and application thereof
CN116003819B (en) * 2023-02-03 2024-01-12 国科大杭州高等研究院 Covalent organic framework material containing imine bond and metal halide perovskite composite material, and preparation method and application thereof

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