CN106450002B - 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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CN106450002B
CN106450002B CN201610996952.2A CN201610996952A CN106450002B CN 106450002 B CN106450002 B CN 106450002B CN 201610996952 A CN201610996952 A CN 201610996952A CN 106450002 B CN106450002 B CN 106450002B
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李建生
王韬
王少杰
崔明月
凌小芳
贾晶晶
王璐瑶
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Tianjin Vocational Institute
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    • H—ELECTRICITY
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/50—Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
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Abstract

The present invention relates to a kind of Ca-Ti ore type opto-electronic conversion composite sols and preparation method thereof, using with photosensitive activity imidodicarbonic diamide and methylamine be mixed with Ca-Ti ore type opto-electronic conversion composite sol, adjust the band gap and filming performance of Ca-Ti ore type light absorbing material.Ca-Ti ore type opto-electronic conversion composite sol of the present invention is made 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 better electronics or holoe carrier transmission performance, can extend the light absorption wavelength range of sunlight and improve the photoelectric conversion efficiency 1.5%-2% of 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 sols 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 conversion efficiency is improved, new energy and field of new materials are belonged to.
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% its photoelectric conversion efficiency at present.Perovskite solar cell is typically by saturating Bright electro-conductive glass, compacted zone, perovskite light absorbing layer, hole transmission layer, five part of metal back electrode composition.Perovskite light absorption The thickness of layer is generally 200-600nm, and main function is to absorb sunlight and generate electron-hole pair, and energy 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.The research of metal cation and halide anion is compared both at home and abroad at present Thoroughly, but to the composition of the ammonium ion of monovalence, structurally and functionally Mechanism Study is seldom 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 A kind of inorganic-organic double salt or complex that iodine methylamine and lead iodide reaction generate, it is also a kind of Semiconductor absorption Material, band gap are about 1.5eV, can fully absorb the visible light of wavelength 400-800nm, system good with absorbing properties Standby simple and high photoelectric conversion efficiency characteristic.Its main deficiency is：（1）Temperature tolerance is bad, it is desirable that the heat treatment of light absorbing layer Temperature is less than 150 DEG C, and the additive during at such a temperature prepared by light absorbing layer cannot decompose completely；（2）Environmental stability is poor, It is easy to decompose for moisture, ultraviolet light or catalyst in air；（3）It absorbs optical wavelength range and is confined to visible region, to ultraviolet light It is hardly picked up with infrared light；（4）Filming performance is bad, is easy to form loose coarse crystalline solid, it is difficult to which large area uniformly applies Cloth.
Improve Ca-Ti ore type light absorbing material performance, design can be formed from Ca-Ti ore type light absorbing material and started with.For example, Or mixtures thereof the primary amine of Chinese Academy of Sciences Qingdao used C1-C4 of biology, carbonamidine prepare perovskite structure light absorbing material, and acquisition is good Good photoelectric conversion efficiency；Xiamen University 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 patent of invention CN105742502 (2016-07-06) is public Exploitation is mixed with the adjustable perovskite structure light absorbing material of band gap with iodobenzene ethamine, stannous iodide and lead iodide；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) is open to prepare calcium titanium with long-chain organic amine Mine structure light absorbing material, but without the details of open long-chain organic amine；United States Patent (USP) US20150200377 (2015- It is 07-16) open to prepare perovskite structure light absorbing material with a series of primary, secondary, uncles, quaternary ammonium compound, but without providing amine The embodiment of compound；Chinese patent CN103554171 (2014-02-05) is open to use 1- aminopyridines azomethine and chlorination Lead cooperation is used 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, can also start with from perovskite light absorbing material structure.For example, Singapore is southern Foreign Polytechnics's patent of invention WO2016126211 (2016-08-11) is open by 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 at 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 as light absorbing material crystal seed and framework material, and one Step obtains the light absorbing layer of smooth even；Nankai University patent of invention CN104218109 (2014-12-17) is open by polyethylene Pyrrolidones is mixed with perovskite light absorbing material, improves the microstructure and filming performance of perovskite light absorbing material, greatly It is big to improve photoelectric conversion 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 that photoelectric conversion efficiency, production cost and battery performance stability, market need photoelectric conversion efficiency Higher perovskite solar cell photoelectric conversion material.
Invention content
The object of the present invention is to provide a kind of Ca-Ti ore type opto-electronic conversion composite sols, from perovskite light absorbing material Composition and two aspect of microstructure, which are started with, improves its filming performance, to adapt to the preparation of large area perovskite solar cell light absorption layer It needs.
The present invention uses, and there is the imidodicarbonic diamide of photosensitive activity and methylamine to be mixed with Ca-Ti ore type opto-electronic conversion composite wood Expect colloidal sol, adjusts Ca-Ti ore type light absorbing material band gap and filming performance, 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 At each component molar 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 material 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 receptor, can be reacted with halogen acids and generate stable salt, energy Enough and metal ion forms ligand or complex compound, and novel inorganic-organic hybrid is generated so can further be reacted with lead halide Ca-Ti ore type photoelectric conversion material, and have 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 reacts generation with halogen acids.
Dehydration catalyst is one of magnesium methoxide, magnesium ethylate, triethyl aluminum or aluminum alkoxide in the present invention, is tried for commercially available chemistry 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 under alkaline condition in colloidal sol of the present invention Nano-particle, nucleus when can form a film as Ca-Ti ore type photoelectric conversion material change material microstructure, prevent photoelectricity from turning Conversion materials form coarse crystallization.
To be dimethylformamide, gamma-butyrolacton or dimethyl sulfoxide (DMSO) mixed with C1-C4 fatty alcohols for organic solvent in the present invention Close object.Dimethylformamide, gamma-butyrolacton or dimethyl sulfoxide (DMSO) polar solvent are for dissolving PbX2、CH3NH3PbX3With RC2O2NH2PbX3, C1-C4 fatty alcohols are commercially available chemical reagent as retarder thinner.
There are halogenation lead molecule, methylamine halogen acid salt molecule and imidodicarbonic diamide halogen acid salt molecule in colloidal sol of the present invention, with And on a small quantity using nanometer oxide particle as the RC of nucleus2O2NH2PbX3And CH3NH3PbX3Micelle or crystal seed, when solvent volatilizees, Coordination, hydrogen bond, Van der Waals force it is common driving under, 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 light region Strong light absorption, and there is higher light and thermally stable.Imidodicarbonic diamide molecule has annular carbonyl structure, and carbonyl is connected with One NH key, this enables imidodicarbonic diamide as weak acid, forms anion under alkaline environment and is coordinated with metal.With solution The increase of alkalinity, the complex that imidodicarbonic diamide is formed with metal ion gradually change to more stable co-ordination state.If using Imidodicarbonic diamide prepares novel Ca-Ti ore type photoelectric conversion material RC instead of methylamine2O2NH2PbX3, will have better electronics or sky Cave carrier transmission performance can reduce the dimensional effect of large area perovskite solar cell, can extend the light to sunlight Absorbing wavelength range and raising photoelectric conversion efficiency.
It is a further object of the present invention to provide a kind of preparation methods of Ca-Ti ore type opto-electronic conversion composite sol, prepare The technical scheme comprises the following steps：
（1）Polar organic solvent, HX and PbX are separately added into glass reactor2, stirred to complete at 60-80 DEG C Dissolving, is then added imide compound, and control raw material molar ratio is：PbX2：HX：Imidodicarbonic diamide=1：1：X, Wherein, x=0.1-0.9 continues to be stirred to react 12-24 h, obtains RC2O2NH2PbX3Solution；
（2）The methanol solution of methylamine is added into the above reaction solution, control raw material molar ratio is：PbX2：HX：First Amine=1：1：1-x continues to be stirred to react 12-24h, is cooled to room temperature, obtains RC2O2NH2PbX3And CH3NH3PbX3It mixes molten Liquid；
（3）Dehydration catalyst is added into the above reaction solution, control raw material molar ratio is：PbX2：Dehydration catalyst = 1：0.02-0.1, dehydration catalyst form nanometer oxide particle colloidal sol, grain size 5- with the reaction of moisture 1-4h in solution 10nm；
（4）C1-C4 fatty alcohols are added into the above reaction solution to PbX2Saturation is precipitated, and so that colloidal sol is become cloudy, then in 90- Flow back 12-24 h at 100 DEG C, and generation contains RC2O2NH2PbX3And CH3NH3PbX3The colloidal sol of crystal seed, the quality of solid in colloidal sol Percentage concentration is 10%-20%；
（5）With biscuit ware funnel secondary filter composite sol, colloidal sol is dropped in the 200mm of compacted zone with dropper It in × 300mm fluorine-doped tin dioxide Conducting Glass, is coated with uniformly with stainless steel wire rod coating device, solvent volatilization is made to dry, Last 110-150 DEG C of heated-air drying 30 minutes, forms the black Ca-Ti ore type light absorbing layer of smooth surface, assembling test calcium titanium Mine solar cell, using RC2O2NH2PbX3And CH3NH3PbX3Composite material is than using merely CH3NH3PbX3Photoelectricity turns when material It changes efficiency and improves 1.5%-2%.
The absorbing properties of photoelectric conversion material film 920 type spectrophotometer test specimens of Lambda in the present invention Absorptivity of the product in 250-1100nm wave-length coverages determines；The assembling of test perovskite solar cell is special with reference to Chinese invention Profit application 2019109316795（2016-10-25）The method of middle use carries 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 Prepared by large area perovskite solar cell light absorption layer needs；
（2）The present invention prepares novel perovskite photoelectric conversion material with the imidodicarbonic diamide with photosensitive activity, has more preferable Electronics or holoe carrier transmission performance, the dimensional effect of large area perovskite thin film solar cell can be reduced；
（3）The present invention is mixed with Ca-Ti ore type photoelectric conversion material with imidodicarbonic diamide and methylamine, can extend to the sun The light absorption wavelength range and raising photoelectric conversion efficiency 1.5%-2% of light.
Specific implementation mode
Embodiment 1
It is separately added into dimethylformamide 365.5g (5mol), quality percentage in the 500mL glass reactors with stirring The hydroiodic acid 30.7g (0.12mol) and lead iodide 46.1g (0.1mol) of concentration 50% stir 2h to complete at 60-80 DEG C Then dissolving is added succimide 4.96g (0.05mol), continues to be stirred to react 24 h, obtain C4H4O2NH2PbI3Solution； The methanol solution 5.18g (0.05mol) for adding the methylamine of mass percentage concentration 30%, continues to be stirred to react 12 h, be cooled to Room temperature obtains C4H4O2NH2PbI3And CH3NH3PbI3Mixed light absorbent solution.
The methanol magnesium solution 29.2g (0.05mol) that mass percentage concentration is 20%, magnesium methoxide are added into the above reaction solution Bitter earth nano colloidal sol, grain size 5nm are formed with reaction of moisture 4h.Absolute ethyl alcohol is continuously added to PbI2Saturation is precipitated, It is in slightly cloudy to make colloidal sol, and then flow back at 90-100 DEG C 24 h, and 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 × It in 300mm fluorine-doped tin dioxide Conducting Glass, is coated with uniformly with stainless steel wire rod coating device, so that solvent volatilization is dried, most 110-150 DEG C of heated-air drying 30 minutes afterwards, forms the black perovskite light absorbing layer of smooth surface, is used as assembling test calcium titanium Mine solar cell, than using simple CH3NH3PbX3Photoelectric conversion efficiency improves 1.5% when material.
Embodiment 2
It is separately added into dimethylformamide 365.5g (5mol), quality percentage in the 500mL glass reactors with stirring The hydroiodic acid 30.7g (0.12mol) and lead iodide 46.1g (0.1mol) of concentration 50% stir 2h to complete at 60-80 DEG C Then dissolving is added phthalimide 2.94g (0.02mol), continues to be stirred to react 24 h, obtain C8H4O2NH2PbI3It is molten Liquid；The methanol solution 8.288g (0.08mol) for adding the methylamine of mass percentage concentration 30% continues to be stirred to react 12 h, cold But room temperature is arrived, C is obtained8H4O2NH2PbI3And CH3NH3PbI3Mixed light absorbent solution.
The aluminium isopropoxide solution 20.4g (0.02mol) that mass percentage concentration is 20%, isopropyl are added into the above reaction solution Aluminium alcoholates forms nano alumina particles colloidal sol, grain size 10nm with reaction of moisture 4h in solution.Continuously add absolute ethyl alcohol extremely PbI2Saturation is precipitated, and it is in slightly cloudy to make colloidal sol, and then flow back at 90-100 DEG C 24 h, and generation contains C8H4O2NH2PbI3With CH3NH3PbI3The colloidal sol of crystal seed.With G5 biscuit ware funnel secondary filter light absorbing material colloidal sols, colloidal sol has been dropped in dropper In 200mm × 300mm fluorine-doped tin dioxide Conducting Glass of compacted zone, it is coated with uniformly, is made with stainless steel wire rod coating device Solvent volatilization is dried, and last 110-150 DEG C of heated-air drying 30 minutes forms the black perovskite light absorbing layer of smooth surface, is used Make assembling test perovskite solar cell, than using simple CH3NH3PbX3Photoelectric conversion efficiency improves 2.0% when 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 mixing reacts with lead halide and prepares Ca-Ti ore type opto-electronic conversion composite material, with adjust Ca-Ti ore type light absorbing material band gap with 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 form, and each component molar 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 described 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 described in claim 1, it is characterised in that dehydration catalyst is methanol 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 The technical scheme comprises the following steps：
（1）Polar organic solvent, HX and PbX are separately added into glass reactor2, stirred at 60-80 DEG C completely molten to solid Solution, is then added imide compound, and control raw material molar ratio is：PbX2：HX：Imidodicarbonic diamide=1:1:X, In, x=0.1-0.9 continues to be stirred to react 12-24 h, obtains RC2O2NH2PbX3Solution；
（2）The methanol solution of methylamine is added into the above reaction solution, control raw material molar ratio is：PbX2：HX：Methylamine= 1:1:1-x continues to be stirred to react 12-24 h, is cooled to room temperature, obtains RC2O2NH2PbX3And CH3NH3PbX3Mixed solution；
（3）Dehydration catalyst is added into the above reaction solution, control raw material molar ratio is：PbX2：Dehydration catalyst=1: 0.02-0.1, dehydration catalyst form nanometer oxide particle colloidal sol, grain size 5-10nm with the reaction of moisture 1-4h in solution；
（4）C1-C4 fatty alcohols are added into the above reaction solution to PbX2Saturation is precipitated, and so that colloidal sol is become cloudy, then at 90-100 DEG C Lower reflux 12-24 h, generation contain RC2O2NH2PbX3And CH3NH3PbX3The colloidal sol of crystal seed, the quality percentage of solid is dense in colloidal sol Degree is 10%-20%；
（5）With biscuit ware funnel secondary filter composite sol, with dropper by colloidal sol drop in the 200mm of compacted zone × It in 300mm fluorine-doped tin dioxide Conducting Glass, is coated with uniformly with stainless steel wire rod coating device, so that solvent volatilization is dried, most 110-150 DEG C of heated-air drying 30 minutes afterwards, forms the black Ca-Ti ore type light absorbing layer of smooth surface, assembling test perovskite Solar cell, using RC2O2NH2PbX3And CH3NH3PbX3Composite material is than using merely CH3NH3PbX3Opto-electronic conversion when material Efficiency improves 1.5%-2%.
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CN110465332A (en) * 2019-07-10 2019-11-19 广东工业大学 A kind of molybdenum disulfide/carbonamidine lead bromate composite photo-catalyst and its preparation method and application
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