CN105514278B - Bimetal complex perovskite materials, preparation method and application thereof - Google Patents
Bimetal complex perovskite materials, preparation method and application thereof Download PDFInfo
- Publication number
- CN105514278B CN105514278B CN201511000522.2A CN201511000522A CN105514278B CN 105514278 B CN105514278 B CN 105514278B CN 201511000522 A CN201511000522 A CN 201511000522A CN 105514278 B CN105514278 B CN 105514278B
- Authority
- CN
- China
- Prior art keywords
- metal composite
- binary metal
- composite perofskite
- layer
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses three bimetal complex perovskite materials AB1B2X3(X: Cl, Br or I) and a preparation method thereof, and an application of the bimetal complex perovskite materials in preparation of perovskite solar cells with multiple structures. The bimetal complex perovskite materials, the preparation method and the application thereof belong to the field of a new-material solar cell. The bimetal complex perovskite material is prepared from an organic halide AX (A: CH3NH3＜+＞, NH2CH=NH2＜+＞; X: Cl＜-＞, Br＜-＞, I＜-＞), metal halides B1X2, B2X2 (B1:Pb＜2+＞, B2: Mg＜2+＞, Ca＜2+＞, Ba＜2+＞, Ba＜2+＞; X: Cl, Br, I), and an organic solvent (N,N-dimethyl formamide DMF, dimethyl sulfoxide DMSO or gamma-butyrrolactone solvent). Compared with existing perovskite materials ABR3 (A: CH3NH3＜-＞, NH2CH=NH2＜+＞; B: Pb＜2+＞; X: Cl＜-＞, Br＜-＞, I＜-＞), the bimetal complex perovskite materials, the preparation method and the application thereof have advantages of effectively content of organic lead ions, reducing environment pollution, and facilitating realization of industrial application of perovskite solar cells.
Description
Technical field
The invention belongs to perovskite technical field of solar batteries is and in particular to three kinds of binary metal composite perofskite materials
(Mg-Pb, Ca-Pb, Ba-Pb) and this application in heterojunction solar battery for three kinds of materials, it is effectively reduced calcium
Toxic heavy metal Pb in titanium ore material2+Content, reduces the harm to environment, is conducive to the extensive industry of the type battery
The application changed.
Background technology
With the increasingly depleted of non-renewable energy resources, being continuously increased of energy resource consumption, energy problem has become as and works as forefathers
The significant challenge that the survival and development of class society face.Solar energy is a kind of inexhaustible, nexhaustible non-polluting energy sources, and too
Sun can battery be then a kind of efficient apparatus that solar energy is converted directly into electric energy using photovoltaic effect.Research and develop efficiently low one-tenth
This novel solar battery, is to realize the wide variety of technical foundation of photovoltaic generation, is also current new energy technology development
Important trend.
In recent years, new perovskite solar battery technology quickly grew.Report from Japanese Scientists Miyasaka in 2009
Road liquid perovskite CH3NH3PbI3The photoelectric transformation efficiency of solar cell 3.8%, to certifications such as Korea S Soek in 2015
20.1% perovskite solar battery efficiency, the lifting of perovskite solar battery efficiency is very swift and violent, cause scientific circles and
The extensive concern of industrial circle.This battery has that raw material sources are extensive, manufacture craft is simple, with low cost and stability is high etc.
Advantage, thus probably become a kind of commercially produced product of great competitiveness in the near future in photovoltaic industry.
In existing perovskite solar cell, as the perovskite material of light-absorption layer, its metal ion usual 100%
By Pb2+Composition, for example：CH3NH3PbI3、NH2CH=NH2PbI3、CH3NH3PbCl3Deng.This perovskite material is because containing a large amount of
Toxic heavy metal Pb2+, there is serious environmental pollution, be unfavorable for the extensive industrialization of perovskite solar cell
Application.Therefore, research and development Mg-Pb, Ca-Pb, Ba-Pb binary metal composite perofskite material is in environmental protection and market-oriented application side
Face is significant.
Content of the invention
For the problem of environmental pollution of current lead halogen perovskite solar cell, the application provides three kinds low lead content calcium titaniums
Pit wood material and preparation method, and the various application processes in area of solar cell, in the photoelectric transformation efficiency ensureing battery
While, promote the environmental friendliness development of perovskite solar cell.
The present invention proposes three kinds of Mg-Pb, Ca-Pb, Ba-Pb composite perofskite materials, and described material is perovskite structure, its
Expression formula can useRepresent, wherein 0<m<1, A isOrOne of；B1For
Pb2+；B2For Mg2+、Ca2+Or Ba2+One of；X is at least Cl-、Br-Or I-One of.
Preferably, described material is by halogenated methyl amine (or halogenation carbonamidine), lead halide, magnesium halide (or calcium halide, halogen
Change calcium), it is dissolved in DMF (DMF), dimethyl sulfoxide (DMSO) (DMSO) or gamma-butyrolacton solvent, then will
Solvent evaporation obtains.
Preferably, in described material, two kinds of metal halide (B1X2、B2X2) material amount sum, with organohalogen compounds
The ratio of the amount of material of (halogenated methyl amine or halogenation carbonamidine) is 1:1～1:3；In described two metal halide admixture,
B1X2(lead halide) proportion is 10～90%, B2X2(magnesium halide, calcium halide or calcium halide) proportion be 90～
10%；Described two metal halide (B1X2、B2X2), organohalogen compounds (halogenated methyl amine or halogenation carbonamidine) be dissolved in N,
In dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) or gamma-butyrolacton solvent, described two metal halides
(B1X2、B2X2), organohalogen compounds (halogenated methyl amine or halogenation carbonamidine) account for 10%～60%, Ran Houtong of solution gross mass
Cross and solvent evaporation is obtained B1-B2(Mg-Pb, Ca-Pb, Ba-Pb) binary metal composite perofskite material.
According to the present invention, there is provided a kind of preparation method of corresponding Mg-Pb, Ca-Pb, Ba-Pb composite perofskite material,
This preparation method comprises the following steps：
(1) under room temperature, by B1X2(lead halide) and B2X2(magnesium halide, calcium halide or calcium halide) presses the ratio of the amount of material
1:9～9:1, mix, form two kinds of metal halide mixed-powders；
(2) by the mixed-powder described in (1), press material with organohalogen compounds (halogenated methyl amine or halogenation carbonamidine) crystal
Amount ratio 1:1～1:3 proportionings, form homogeneous mixture；
(3) at room temperature～130 DEG C, described to (2) mixture is dissolved in DMF (DMF), dimethyl
In sulfoxide (DMSO) or gamma-butyrolacton solvent, stir and dissolve to whole, then pass through in 5 points of 60 DEG C～150 DEG C heating anneals
Solvent is evaporated by clock～120 minute, you can obtain B1-B2(Mg-Pb, Ca-Pb, Ba-Pb) binary metal composite perofskite material.
Preferably, described halogenated methyl amine is CH3NH3Cl、CH3NH3Br or CH3NH3One kind of I；Described halogenation carbonamidine
It is NH2CH=NH2Cl、NH2CH=NH2Br or NH2CH=NH2One kind of I；Described lead halide is PbCl2、PbBr2Or PbI2
One kind；Described magnesium halide is MgCl2、MgBr2Or MgI2One or more of mixing.Described calcium halide is CaCl2、
CaBr2Or CaI2One or more of mixing.Described barium halide is BaCl2、BaBr2Or BaI2One or more of mixed
Close.
New binary metal composite perofskite material proposed by the present invention, can apply the perovskite solar energy in various structures
In battery.It is another aspect of this invention to provide that the present invention is further illustrated five kinds by above-mentioned binary metal composite perofskite
Material is used for the manufacture method of solar cell.
The present invention provides the first to apply the method that solar cell prepared by above-mentioned binary metal composite perofskite material, bag
Include following steps：
The preparation of step (1) hole blocking layer
On the electro-conductive glass having plated fluorine doped tin oxide FTO, under the conditions of 400 DEG C～600 DEG C, by 0.01mol/L～
The isopropyl titanate aqueous isopropanol of 0.05mol/L, deposits the thick fine and close TiO of 20nm～100nm by the method for thermal spraying2Empty
Cave barrier layer；
The preparation of step (2) electron transfer layer
In described TiO2On barrier layer, by the TiO that serigraphy 200nm～1000nm is thick2Nano-particle layer, at 450 DEG C
Under the conditions of～550 DEG C, anneal 0.5 hour～2 hours, form the mesoporous TiO of 200nm～1000nm2Electron transfer layer；
The preparation of the mesoporous insulating barrier of step (3)
A diameter of 10nm～50nm ZrO will be included2Nano particle or Al2O3The slurry of nano particle, by silk screen
Printing on the electron transport layer, under the conditions of 450 DEG C～550 DEG C, sinters 0.5 hour～2 hours, forms 200nm～1000nm
Mesoporous insulating barrier；
The preparation to electrode for step (4) carbon
Will be by nano carbon black, graphite powder and ZrO2The carbon pastes of nano adhesive composition, mesoporous exhausted by being screen printed onto
In edge layer, under the conditions of 400 DEG C～500 DEG C, sinter 0.5 hour～2 hours, form the carbon that thickness is 5 μm～20 μm to electrode；
Step (5) fills binary metal composite perofskite material
Described binary metal composite perofskite material is heated to 50 DEG C～130 DEG C, take 1 μ L～100 μ L drop in described in too
The carbon of sun energy battery, to electrode surface, is then heated 10 minutes～120 minutes with 60 DEG C～150 DEG C temperature, makes this kind of binary gold
Belong to the volatilization of composite perofskite material solvent, obtain the binary metal composite perofskite solar cell of solid-state.
The present invention provides second to apply the method that solar cell prepared by above-mentioned binary metal composite perofskite material, bag
Include following steps：
The preparation of step (1) hole blocking layer
On the electro-conductive glass having plated fluorine doped tin oxide FTO, under the conditions of 400 DEG C～600 DEG C, by 0.01mol/L～
The isopropyl titanate aqueous isopropanol of 0.05mol/L, deposits the thick fine and close TiO of 20nm～100nm by the method for thermal spraying2Empty
Cave barrier layer；
The preparation of step (2) electron transfer layer
On the described barrier layer preparing, the thick TiO of one layer of 50nm～500nm of serigraphy2Nano particle, 450
DEG C～550 DEG C under the conditions of, anneal 0.5 hour～2 hours, form the mesoporous TiO of one layer of about 50nm～500nm2Electron transfer layer；
The preparation of step (3) binary metal composite perofskite material light-absorption layer
Take binary metal composite perofskite solution spin coating described in 50 μ L～1000 μ L on the electron transport layer, 70 DEG C～
Under the conditions of 150 DEG C, heat 10 minutes～120 minutes, so that binary metal composite perofskite material solvent is volatilized and form one layer of 200nm
The binary metal composite perofskite material light-absorption layer of～1000nm；
The preparation of step (4) hole transmission layer
By P3HT (or Spiro-MeOTAD, PTAA, CuI, CuSCN solution), it is spin-coated on described perovskite light-absorption layer
On, form 50nm～200nm hole transmission layer；
The preparation to electrode for step (5) metal
Using vacuum evaporation coating film device, evaporation a layer thickness is the Au of 60nm～150nm on the hole transport layer
Or Ag electrode, obtain the binary metal composite perofskite solar cell of solid-state.
The present invention provides the third application method that solar cell prepared by above-mentioned binary metal composite perofskite material,
Comprise the following steps：
The preparation of step (1) hole blocking layer
On the electro-conductive glass having plated fluorine doped tin oxide FTO, under the conditions of 400 DEG C～600 DEG C, by 0.01mol/L～
The isopropyl titanate aqueous isopropanol of 0.05mol/L, deposits the thick fine and close TiO of 20nm～100nm by the method for thermal spraying2Empty
Cave barrier layer；
The preparation of step (2) binary metal composite perofskite material light-absorption layer
Take the binary metal composite perofskite solution described in 50 μ L～1000 μ L to be spin-coated on hole blocking layer, 70 DEG C～
Under the conditions of 150 DEG C, heat 10 minutes～120 minutes, so that binary metal composite perofskite material solvent is volatilized and form one layer of 200nm
The binary metal composite perofskite material light-absorption layer of～1000nm；
The preparation of step (3) hole transmission layer
By P3HT (or Spiro-MeOTAD, PTAA, CuI, CuSCN solution), it is spin-coated on described perovskite light-absorption layer
On, form 50nm～200nm hole transmission layer；
The preparation to electrode for step (4) metal
Using vacuum evaporation coating film device, evaporation a layer thickness is the Au of 60nm～150nm on the hole transport layer
Or Ag electrode, obtain the binary metal composite perofskite solar cell of solid-state.
The present invention provides the method that solar cell prepared by the 4th kind of above-mentioned binary metal composite perofskite material of application,
Comprise the following steps：
The preparation of step (1) electronic barrier layer
On the electro-conductive glass having plated fluorine doped tin oxide FTO, under the conditions of 400 DEG C～600 DEG C, by 0.005mol/L～
The nickel acetylacetonate acetonitrile solution of 0.05mol/L, deposits the thick fine and close NiO electronics resistance of 10nm～50nm by the method for thermal spraying
Barrier；
The preparation of step (2) binary metal composite perofskite material light-absorption layer
Take the binary metal composite perofskite solution described in 50 μ L～1000 μ L to be spin-coated on electronic barrier layer, 70 DEG C～
Under the conditions of 150 DEG C, heat 10 minutes～120 minutes, so that binary metal composite perofskite material solvent is volatilized and form one layer of 200nm
The binary metal composite perofskite light-absorption layer of～1000nm；
The preparation of step (3) electron transfer layer
Heat at 70 DEG C～100 DEG C after PCBM solution is spin-coated on described perovskite light-absorption layer, form one layer of 50nm
The electron transfer layer of～200nm；
The preparation of step (4) interface-modifying layer
By BCP, LiF, TiOxOr the material such as Ca passes through spin coating or evaporation on the electron transport layer, form one layer of 1nm
～20nm interface-modifying layer；
The preparation to electrode for step (5) metal
On interface-modifying layer, evaporation a layer thickness is Al the or Ag electrode of 60nm～150nm, obtains the binary gold of solid-state
Belong to composite perofskite solar cell.
The present invention provides the method that solar cell prepared by the 5th kind of above-mentioned binary metal composite perofskite material, including
Following steps：
The preparation of step (1) hole transmission layer
By PEDOT:PSS solution is spin-coated on the ito glass cleaning up, and forms one layer of 20nm～100nm hole transport
Layer；
The preparation of step (2) binary metal composite perofskite material light-absorption layer
Take the binary metal composite perofskite solution described in 50 μ L～1000 μ L to be spin-coated on hole transmission layer, 70 DEG C～
Under the conditions of 150 DEG C, heat 10 minutes～120 minutes, so that binary metal composite perofskite material solvent is volatilized and form one layer of 200nm
The binary metal composite perofskite material light-absorption layer of～1000nm；
The preparation of step (3) electron transfer layer
Heat at 70 DEG C～100 DEG C after PCBM solution is spin-coated on described perovskite light-absorption layer, form one layer of 50nm
The electron transfer layer of～200nm；
The preparation of step (4) interface-modifying layer
By BCP, LiF, TiOxOr the material such as Ca passes through spin coating or evaporation on the electron transport layer, form one layer of 1nm
～20nm interface-modifying layer；
The preparation to electrode for step (5) metal
On interface-modifying layer, evaporation a layer thickness is Al the or Ag electrode of 60nm～150nm, obtains the binary gold of solid-state
Belong to composite perofskite solar cell.
In general, according to the binary metal composite perofskite material of the present invention, (structural formula isWherein
0<m<1, A isOrOne of；B1For Pb2+；B2For Mg2+、Ca2+Or Ba2+One of；X is extremely
It is Cl less-、Br-Or I-One of.) and existing lead halogen perovskite material (CH3NH3PbI3、NH2CH=NH2PbI3Deng) compare,
Advantage is：Magnesium halide, calcium halide, barium halide raw material are easy to get inexpensively.With Mg2+、Ca2+、Ba2+Part replaces existing lead halogen calcium titanium
Toxic heavy metal Pb in pit wood material2+, while ensureing battery items photoelectric properties, greatly reduce to environment and human body
Harm, is conducive to promoting the extensive commercial application of perovskite solar cell.
Brief description
Fig. 1 is CH obtained by embodiment 13NH3Pb1-xMgxI3The XRD of perovskite thin film；
Fig. 2 is CH obtained by embodiment 23NH3Pb1-xCaxI3The XRD of perovskite thin film；
Fig. 3 is CH obtained by embodiment 33NH3Pb1-xBaxI3The XRD of perovskite thin film；
Fig. 4 is CH obtained by embodiment 23NH3Pb1-xCaxI3The UV-vis absorption spectrum figure of perovskite thin film；
Fig. 5 is perovskite solar battery structure schematic diagram, wherein, 1 electrically conducting transparent substrate, 2 hole blocking layers, 3 electronics
Transport layer, 4 porous dielectric layers and 5 carbon are to electrode；
Fig. 6 is perovskite solar battery structure schematic diagram, wherein, 1 electrically conducting transparent substrate, 2 hole blocking layers, 3 electronics
Transport layer, 6 perovskite light-absorption layers, 7 hole transmission layers and 8 metals are to electrode；
Fig. 7 is perovskite solar battery structure schematic diagram, wherein, 1 electrically conducting transparent substrate, 2 hole blocking layers, 6 calcium titaniums
Ore deposit light-absorption layer, 7 hole transmission layers and 8 metals are to electrode；
Fig. 8 is perovskite solar battery structure schematic diagram, wherein, 1 electrically conducting transparent substrate, 9 electronic barrier layers, 6 calcium titaniums
Ore deposit light-absorption layer, 3 electron transfer layers, 10 interface-modifying layer and 8 metals are to electrode；
Fig. 9 is perovskite solar battery structure schematic diagram, wherein, 1 electrically conducting transparent substrate, 7 hole transmission layers, 6 calcium titaniums
Ore deposit light-absorption layer, 3 electron transfer layers, 10 interface-modifying layer, 8 metals are to electrode；
Figure 10 is the current density voltage curve figure of perovskite solar cell obtained by embodiment 4；
Figure 11 is the current density voltage curve figure of perovskite solar cell obtained by embodiment 5；
Figure 12 is the current density voltage curve figure of perovskite solar cell obtained by embodiment 6；
Figure 13 is the current density voltage curve figure of perovskite solar cell obtained by embodiment 7；
Figure 14 is the current density voltage curve figure of perovskite solar cell obtained by embodiment 8.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, below in conjunction with drawings and Examples, right
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only in order to explain the present invention, and
It is not used in the restriction present invention.
Embodiment 1, comprises the steps：
(1) under room temperature, by PbI2With MgI2The ratio that powder presses the amount of material is 9:1 uniformly mixes；
(2) by the mixed-powder described in (1), with CH3NH3I crystal presses the ratio 1 of the amount of material:1 proportioning, forms and uniformly mixes
Thing；
(3) mixture described in (2) is dissolved in DMF (DMF) solvent, stirs under room temperature, until
All dissolve, obtain CH3NH3Pb0.9Mg0.1I3Composite perofskite solution；
(4) solution taking 2ml (3) to obtain, is screwed on sheet glass, then in 60 DEG C of heating anneals 120 minutes by solvent
It is evaporated, obtain CH3NH3Pb0.9Mg0.1I3Composite perofskite thin-film material.
Embodiment 2, comprises the steps：
(1) under room temperature, by PbI2With CaI2The ratio that powder presses the amount of material is 9:1 uniformly mixes；
(2) by the mixed-powder described in (1), with CH3NH3I crystal presses the ratio 1 of the amount of material:2 proportionings, form and uniformly mix
Thing；
(3) mixture described in (2) is dissolved in dimethyl sulfoxide (DMSO) (DMSO) solvent, stirs at 100 DEG C, until all
Dissolving, obtains CH3NH3Pb0.9Ca0.1I3Composite perofskite solution；
(4) solution taking 2ml (3) to obtain, is screwed on sheet glass, then in 100 DEG C of heating anneals 60 minutes by solvent
It is evaporated, obtain CH3NH3Pb0.9Ca0.1I3Composite perofskite thin-film material.
Embodiment 3, comprises the steps：
(1) under room temperature, by PbI2With BaI2The ratio that powder presses the amount of material is 9:1 uniformly mixes；
(2) by the mixed-powder described in (1), with CH3NH3I crystal presses the ratio 1 of the amount of material:3 proportionings, form and uniformly mix
Thing；
(3) mixture described in (2) is dissolved in gamma-butyrolacton solvent, stirs at 130 DEG C, until whole dissolve, obtain
To CH3NH3Pb0.9Ba0.1I3Composite perofskite solution；
(4) solution taking 2ml (3) to obtain, is screwed on sheet glass, then steams solvent within 5 minutes in 150 DEG C of heating anneals
Dry, obtain CH3NH3Pb0.9Ba0.1I3Composite perofskite thin-film material.
Embodiment 4, comprises the steps：
(1) cleaning step：Selection sheet resistance is 5～25 Ω, and transmitance is substrate in 70～90% FTO glass, Ran Houyi
Secondary liquid detergent, distilled water, ethanol and acetone clean；
(2) preparation of hole blocking layer：On the electro-conductive glass having plated fluorine doped tin oxide FTO, under the conditions of 460 DEG C, will
The isopropyl titanate aqueous isopropanol of 0.05mol/L, deposits the thick fine and close TiO of 20nm by the method for thermal spraying2Hole barrier
Layer.Continue after the completion of spraying to anneal at such a temperature 2 hours；
(3) electron transfer layer preparation process：In described TiO2On barrier layer, by the TiO that serigraphy 500nm is thick2Nanometer
Stratum granulosum, under the conditions of 500 DEG C, anneals 2 hours, forms the mesoporous TiO of 500nm2Electron transfer layer；
(4) mesoporous insulating barrier preparation process：A diameter of 50nm Al will be included2O3The slurry of nano particle, by silk screen
Printing on the electron transport layer, sinters 2 hours at 500 DEG C, forms the mesoporous insulating barrier of 1000nm；
(5) carbon is to electrode preparation process：Will be by nano carbon black, graphite powder and ZrO2The carbon pastes of nano adhesive composition are used
The mode double exposure of serigraphy, on described mesoporous insulating barrier, under the conditions of 400 DEG C, sinters 1 hour, forming thickness is 10 μm
Carbon is to electrode；
(6) Ca-Pb binary metal composite perofskite solution preparation step is with (1)～(3), wherein PbI of embodiment 22:
CaI2It is respectively 9:1、8:2、7:3、6:4、5:5；
(7) fill Ca-Pb binary metal composite perofskite：In the carbon of described solar cell, 2 μ L are instilled to electrode surface
Ca-Pb binary metal composite perofskite solution after heating, heats 30 minutes at 75 DEG C, so that solvent is volatilized and obtains solid-state
Ca-Pb binary metal composite perofskite solar cell.
Embodiment 5, comprises the steps：
(1) cleaning step：Selection sheet resistance is 5～25 Ω, and transmitance is substrate in 70～90% FTO glass, Ran Houyi
Secondary liquid detergent, distilled water, ethanol and acetone clean；
(2) preparation process of hole blocking layer：On the electro-conductive glass having plated fluorine doped tin oxide FTO, under the conditions of 500 DEG C,
By the isopropyl titanate aqueous isopropanol of 0.01mol/L, the thick fine and close TiO of 100nm is deposited by the method for thermal spraying2Hole hinders
Barrier；
(3) preparation process of electron transfer layer：On the described barrier layer preparing, one layer of 150nm thickness of serigraphy
TiO2Nano particle, under the conditions of 550 DEG C, anneals 1.5 hours, the mesoporous TiO of one layer of about 150nm of formation2Electron transfer layer；
(4) Mg-Pb binary metal composite perofskite solution preparation step：By PbI2With MgBr2Form mixture, wherein
PbI2Accounting for mol ratio is 70%, CH3NH3I and this mixture in molar ratio 1:2 are dissolved in gamma-butyrolacton solvent, at 120 DEG C
Stirring, until whole dissolve, obtains Mg-Pb binary metal composite perofskite solution；
(5) preparation process of Mg-Pb binary metal composite perofskite material light-absorption layer：Take the Mg-Pb binary described in 150 μ L
Metal composite perovskite solution spin coating on the electron transport layer, under the conditions of 100 DEG C, is heated 30 minutes, is formed after solvent volatilization
The Mg-Pb binary metal composite perofskite material light-absorption layer of one layer of 100nm；
(6) preparation process of hole transmission layer：With having configured P3HT, it is spin-coated on perovskite light-absorption layer, formed about
100nm hole transmission layer；
(7) preparation process to electrode for the metal：Using vacuum evaporation coating film device, it is deposited with one on the hole transport layer
Thickness degree is the Au electrode of 60nm, obtains the binary metal composite perofskite solar cell of solid-state.
Embodiment 6, comprises the steps：
(1) cleaning step：Selection sheet resistance is 5～25 Ω, and transmitance is substrate in 70～90% FTO glass, Ran Houyi
Secondary liquid detergent, distilled water, ethanol and acetone clean；
(2) preparation process of hole blocking layer：On the electro-conductive glass having plated fluorine doped tin oxide FTO, under the conditions of 600 DEG C,
By the isopropyl titanate aqueous isopropanol of 0.25mol/L, the thick fine and close TiO of 100nm is deposited by the method for thermal spraying2Hole hinders
Barrier；
(3) Ba-Pb binary metal composite perofskite solution preparation step：By PbI2With BaCl2Form mixture, wherein
PbI2Accounting for mol ratio is 70%, CH3NH3I and this mixture in molar ratio 1:1 is dissolved in gamma-butyrolacton solvent, at 120 DEG C
Stirring, until whole dissolve, obtains Ba-Pb binary metal composite perofskite solution；
(4) preparation of Ba-Pb binary metal composite perofskite material light-absorption layer：Take the Ba-Pb binary metal described in 100 μ L
Composite perofskite solution is spin-coated on hole blocking layer, under the conditions of 120 DEG C, heats 30 minutes, forms one layer after solvent volatilization
The Ba-Pb binary metal composite perofskite light-absorption layer of 500nm；
(5) preparation process of hole transmission layer：By the Spiro-MeOTAD having configured, it is spin-coated on described perovskite extinction
On layer, form about 100nm hole transmission layer；
(6) preparation to electrode for the metal：Using vacuum evaporation coating film device, it is deposited with thick layer on the hole transport layer
Spend the Ag electrode for 60nm, obtain the binary metal composite perofskite solar cell of solid-state.
Embodiment 7, comprises the steps：
(1) cleaning step：Selection sheet resistance is 5～25 Ω, and transmitance is substrate in 70～90% FTO glass, Ran Houyi
Secondary liquid detergent, distilled water, ethanol and acetone clean；
(2) preparation process of electronic barrier layer：On the electro-conductive glass having plated fluorine doped tin oxide FTO, under the conditions of 500 DEG C,
By the nickel acetylacetonate acetonitrile solution of 0.025mol/L, the thick fine and close NiO electronic blocking of 50nm is deposited by the method for thermal spraying
Layer；
(3) Ca-Pb binary metal composite perofskite solution preparation step：By PbI2With CaI2Form mixture, wherein PbI2
Accounting for mol ratio is 80%, NH2CH=NH2I and this mixture in molar ratio 1:1 is dissolved in N,N-dimethylformamide DMF solvent
In, stir at 80 DEG C, until whole dissolve, obtain Ca-Pb binary metal composite perofskite solution；
(4) preparation process of Ca-Pb binary metal composite perofskite material light-absorption layer：Take the Ca-Pb binary described in 50 μ L
Metal composite perovskite solution is spin-coated on electronic barrier layer, under the conditions of 70 DEG C, heats 100 minutes, after solvent volatilization, is formed
The binary metal composite perofskite light-absorption layer of one layer of 200nm；
(5) preparation process of electron transfer layer：After PCBM solution is spin-coated on described perovskite light-absorption layer, it is placed on 70
Heat at DEG C, form the electron transfer layer of one layer of 50nm；
(6) preparation process of interface-modifying layer：BCP is passed through spin coating or is deposited with the electron transport layer, form one
Layer 1nm interface-modifying layer；
(7) preparation process to electrode for the metal：On interface-modifying layer, evaporation a layer thickness is the Al electrode of 60nm, obtains
The binary metal composite perofskite solar cell of solid-state.
Embodiment 8, comprises the steps：
(1) cleaning step：Selection sheet resistance is 5～25 Ω, and transmitance is substrate in 70～90% FTO glass, Ran Houyi
Secondary liquid detergent, distilled water, ethanol and acetone clean；
(2) preparation process of hole transmission layer：By PEDOT:PSS solution is spin-coated on the ito glass cleaning up, and 100
DEG C annealing formed one layer of 20nm hole transmission layer；
(3) Ba-Pb binary metal composite perofskite material preparation process：By PbI2With BaCl2Form mixture, wherein
PbI2Accounting for mol ratio is 80%, NH2CH=NH2I and this mixture in molar ratio 1:1 to be dissolved in N,N-dimethylformamide DMF molten
In agent, stir at 100 DEG C, until whole dissolve, obtain Ba-Pb binary metal composite perofskite solution；
(4) preparation process of Ba-Pb binary metal composite perofskite material light-absorption layer：Take the Ba-Pb binary described in 800 μ L
Metal composite perovskite solution is spin-coated on hole transmission layer, under the conditions of 100 DEG C, heats 30 minutes, is formed after solvent volatilization
The binary metal composite perofskite material light-absorption layer of one layer of 1000nm；
(5) preparation process of electron transfer layer：After PCBM solution is spin-coated on described perovskite light-absorption layer at 70 DEG C
Heating 30 minutes, forms the electron transfer layer of one layer of 60nm；
(6) preparation process of interface-modifying layer：BCP is passed through spin coating or is deposited with the electron transport layer, form one
Layer 10nm interface-modifying layer；
(7) preparation process to electrode for the metal：On interface-modifying layer, evaporation a layer thickness is the Ag electrode of 60nm, obtains
The binary metal composite perofskite solar cell of solid-state.
As it will be easily appreciated by one skilled in the art that the foregoing is only presently preferred embodiments of the present invention, not in order to
Limit the present invention, all any modification, equivalent and improvement made within the spirit and principles in the present invention etc., all should comprise
Within protection scope of the present invention.
Claims (7)
1. a kind of binary metal composite perofskite materials A B1B2X3It is characterised in that described binary metal composite perofskite material
For perovskite structure, the expression formula of described binary metal composite perofskite material isWherein 0<m<1, A is +OrOne of；B1For Pb2+；B2For Mg2+、Ca2+Or Ba2+One of；X is at least Cl-、
Br-Or I-One of.
2. binary metal composite perofskite material as claimed in claim 1 is it is characterised in that B1X2、B2X2Two kinds of metal halides
The amount sum of the material of thing, with CH3NH3X or NH2CH=NH2The ratio of the amount of the material of X is 1:1～1:3.
3. binary metal composite perofskite material as claimed in claim 1 is it is characterised in that two kinds of metal halide admixture
In, B1X2Proportion is 10～90%, B2X2Proportion is 90～10%.
4. a kind of preparation method of binary metal composite perofskite material is it is characterised in that comprise the steps：
(1) at room temperature by B1X2With B2X2Ratio 1 by the amount of material:9～9:1 mixes, and forms two kinds of metal halides and mixes
Close powder；Wherein, B1X2For lead halide, B2X2For one of magnesium halide, calcium halide or barium halide；
(2) described mixed-powder and organohalogen compounds crystal are pressed the ratio 1 of the amount of material:1～1:3 proportionings, form and uniformly mix
Thing；Wherein, organohalogen compounds are halogenated methyl amine or halogenation carbonamidine；
(3) at room temperature～130 DEG C, by described mixture be dissolved in DMF DMF, dimethyl sulfoxide (DMSO) DMSO or
In person's gamma-butyrolacton solvent, stir and dissolve to whole, then pass through in 60 DEG C～150 DEG C heating anneals 5 minutes～120 minutes
Solvent is evaporated, you can obtain B1-B2Binary metal composite perofskite material；Wherein, described B1-B2For Mg-Pb, Ca-Pb or
Ba-Pb.
5. preparation method as claimed in claim 4 is it is characterised in that described halogenated methyl amine is CH3NH3Cl、CH3NH3Br or
Person CH3NH3One kind of I；Described halogenation carbonamidine is NH2CH=NH2Cl、NH2CH=NH2Br or NH2CH=NH2One kind of I；Institute
Stating lead halide is PbCl2、PbBr2Or PbI2One kind；Described magnesium halide is MgCl2、MgBr2Or MgI2One or more of
Mixing；Described calcium halide is CaCl2、CaBr2Or CaI2One or more of mixing；Described barium halide is BaCl2、
BaBr2Or BaI2One or more of mixing.
6. a kind of application based on the binary metal composite perofskite material described in claim 1.
7. a kind of solar cell based on the binary metal composite perofskite material described in claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511000522.2A CN105514278B (en) | 2015-12-24 | 2015-12-24 | Bimetal complex perovskite materials, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511000522.2A CN105514278B (en) | 2015-12-24 | 2015-12-24 | Bimetal complex perovskite materials, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105514278A CN105514278A (en) | 2016-04-20 |
| CN105514278B true CN105514278B (en) | 2017-02-22 |
Family
ID=55722101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201511000522.2A Active CN105514278B (en) | 2015-12-24 | 2015-12-24 | Bimetal complex perovskite materials, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105514278B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017221834A1 (en) * | 2016-06-24 | 2017-12-28 | 住友化学株式会社 | Composition |
| CN107170887B (en) * | 2017-03-22 | 2019-06-28 | 宁波大学 | One kind having BaCl2The perovskite solar battery and its manufacturing method of decorative layer |
| CN108855775A (en) * | 2018-06-30 | 2018-11-23 | 浙江浙能技术研究院有限公司 | The coating process and device of perovskite light-absorption layer in a kind of perovskite solar battery |
| CN113285027B (en) * | 2021-05-20 | 2023-06-06 | 南京信息工程大学 | Two-dimensional perovskite thin film material, solar cell and preparation method thereof |
| CN116103043B (en) * | 2023-02-16 | 2024-02-23 | 中国科学技术大学 | CsPbBr for passivating surface defects 3-x Cl x Perovskite nanocrystalline as well as preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103346018B (en) * | 2013-06-26 | 2016-08-17 | 中国科学院青岛生物能源与过程研究所 | Be there is the iodide solaode of perovskite structure by solid-liquid reaction preparation |
| CN104091888B (en) * | 2014-07-17 | 2016-08-17 | 湖北大学 | A kind of Ca-Ti ore type solaode and preparation method thereof |
| CN105070832A (en) * | 2015-07-07 | 2015-11-18 | 华中科技大学 | Sr-Pb binary metal composite perovskite material, and preparation and application method thereof |
| CN105070834B (en) * | 2015-07-28 | 2016-06-01 | 华中科技大学 | A kind of uhligite solar cell based on doping type NiO hole transmission layer and its preparation method |
-
2015
- 2015-12-24 CN CN201511000522.2A patent/CN105514278B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105514278A (en) | 2016-04-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105514278B (en) | Bimetal complex perovskite materials, preparation method and application thereof | |
| Cotella et al. | One-step deposition by slot-die coating of mixed lead halide perovskite for photovoltaic applications | |
| Meng et al. | Current progress in interfacial engineering of carbon-based perovskite solar cells | |
| Fan et al. | Perovskite-based low-cost and high-efficiency hybrid halide solar cells | |
| Qin et al. | Recent progress in stability of perovskite solar cells | |
| CN107204379B (en) | A kind of inorganic perovskite thin film of high quality and preparation method thereof and application in solar cells | |
| Qin et al. | The optimum titanium precursor of fabricating TiO 2 compact layer for perovskite solar cells | |
| Li et al. | Recent progress towards roll-to-roll manufacturing of perovskite solar cells using slot-die processing | |
| Pan et al. | Laser annealed composite titanium dioxide electrodes for dye-sensitized solar cells on glass and plastics | |
| EP2994946B1 (en) | Method of manufacturing photovoltaic device using perovskites | |
| CN105070832A (en) | Sr-Pb binary metal composite perovskite material, and preparation and application method thereof | |
| CN108470835A (en) | Perovskite solar cell and preparation method thereof based on two-dimentional transition metal carbide or nitride | |
| CN105070834A (en) | Perovskite solar cell based on doped NiO hole transport layer and preparation method thereof | |
| CN106384785B (en) | A kind of tin dope methyl ammonium lead iodide perovskite solar cell | |
| Saeed et al. | 2D MXene: a potential candidate for photovoltaic cells? A critical review | |
| CN107275494A (en) | A kind of flexible perovskite solar cell scrapes coating preparation method | |
| CN105702864A (en) | High quality perovskite thin film, solar cell and preparation method thereof | |
| Deng et al. | Highly bright Li (Gd, Y) F4: Yb, Er upconverting nanocrystals incorporated hole transport layer for efficient perovskite solar cells | |
| Chen et al. | Stabilizing and scaling up carbon-based perovskite solar cells | |
| CN101840795A (en) | Flexible dye-sensitized solar cell | |
| CN105304820A (en) | Perovskite solar cell with enhanced graphene and preparation method thereof | |
| Yang et al. | High efficient and long-time stable planar heterojunction perovskite solar cells with doctor-bladed carbon electrode | |
| Samantaray et al. | Recent development and directions in printed perovskite solar cells | |
| Mashreghi et al. | Improving perovskite/carbon interfacial contact in carbon based perovskite solar cells by changing two-step spin coating sequence | |
| CN105280822A (en) | Low-cost solar cell suitable for production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |