CN107141221A - A kind of perovskite structural material and preparation method thereof, application - Google Patents
A kind of perovskite structural material and preparation method thereof, application Download PDFInfo
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- CN107141221A CN107141221A CN201710330709.1A CN201710330709A CN107141221A CN 107141221 A CN107141221 A CN 107141221A CN 201710330709 A CN201710330709 A CN 201710330709A CN 107141221 A CN107141221 A CN 107141221A
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Abstract
The present invention discloses a kind of perovskite structural material and preparation method thereof, application, wherein, the chemical formula of the fluorine-containing perovskite structural material is RNH3MX3‑aYa, wherein, R is fluoro-alkyl, and M is metallic element, and X and Y are respectively any one in Cl, Br or I, 0≤a≤3；The fluorine-containing perovskite structural material that the present invention is provided, fluorine element instead of the part protium on alkyl so that the fluorine-containing perovskite structural material of preparation has stronger hydrophobic performance, and performance stable in the air is stronger, it is difficult to be oxidized, area of solar cell can be widely used in.
Description
Technical field
The present invention relates to field of photovoltaic materials, more particularly to a kind of perovskite structural material and preparation method thereof, application.
Background technology
With gradually exhausting for global warming and fossil energy, it is always the mankind to clean reproducible novel energy
The target of pursuit.Solar energy, as inexhaustible clean energy resource, is always the focus of people's research.Solar-electricity
Pond is the device for directly converting the solar into electric energy, from traditional silicon solar cell again at present with dye sensitization of solar
Battery and organic solar batteries are obtained for for the novel battery of representative to be developed rapidly.
All solid state perovskite sensitization solar battery was quickly grown at nearly 2 years, as an international study hotspot；
However, the perovskite structural material that is prepared using methyl iodide first ammonia as perovskite presoma at present, intolerant to water oxygen, pole is not in atmosphere
Stable, this greatly limits the application and popularizations of perovskite structural material.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide a kind of fluorine-containing perovskite structural material and its
Preparation method, application, it is intended to solve existing perovskite structural material intolerant to water oxygen, it is extremely unstable in atmosphere, cause it to apply
Limited the problem of.
Technical scheme is as follows：
A kind of fluorine-containing perovskite structural material, wherein, the chemical formula of the fluorine-containing perovskite structural material is RNH3MX3-aYa, its
In, R is fluoro-alkyl, and M is metallic element, and X and Y are respectively any one in Cl, Br or I, 0≤a≤3.
Described fluorine-containing perovskite structural material, wherein, in the fluoro-alkyl, 1≤C Ge Shuo≤12.
Described fluorine-containing perovskite structural material, wherein, the M is Pb2+、Ge2+、Sn2+、Cu2+、Ni2+、Co2+、Fe2+、
Mn2+、Cr2+、Pd2+、Cd2+、Eu2+Or Yb2+In one kind.
As above a kind of preparation method of any described fluorine-containing perovskite structural material, wherein, including step：
The preparation of presoma：Fluoro-alkyl ammonia is mixed by a certain percentage with HX and is dissolved in organic solvent, after the stirring scheduled time
Decompression screws out solvent, and drying obtains presoma；
The preparation of perovskite structural material：By the presoma and MY2Mixing is dissolved in organic solvent, is precipitated after stirring,
The fluorine-containing perovskite structural material is made in the precipitation drying.
The preparation method of described fluorine-containing perovskite structural material, wherein, in the preparation process of presoma, the fluoro
Alkyl is 1 with HX mol ratios：2.01-1：2.1.
The preparation method of described fluorine-containing perovskite structural material, wherein, it is described organic in the preparation process of presoma
Solvent is absolute ethyl alcohol.
The preparation method of described fluorine-containing perovskite structural material, wherein, in the preparation process of presoma, when solvent rotation
After going out, obtained white powder is washed three times with ether, is dried in vacuum overnight at 60 DEG C, obtains presoma.
The preparation method of described fluorine-containing perovskite structural material, wherein, in the preparation process of presoma, mixing time
For 1-3h.
The preparation method of described fluorine-containing perovskite structural material, wherein, in the preparation process of perovskite structural material,
The organic solvent is dimethylformamide.
As above a kind of application of any described fluorine-containing perovskite structural material, wherein, the fluorine-containing perovskite structure material
Expect for the light-absorption layer in solar cell device.
Beneficial effect：The fluorine-containing perovskite structural material that the present invention is provided, fluorine element instead of the part hydrogen member on alkyl
Element so that the fluorine-containing perovskite structural material of preparation has stronger hydrophobic performance, and performance stable in the air is stronger, be difficult by
Oxidation, can be widely used in area of solar cell.
Brief description of the drawings
Fig. 1 is a kind of flow chart of the preparation method preferred embodiment of fluorine-containing perovskite structural material of the present invention；
The structural representation for the solar cell device preferred embodiment that Fig. 2 is prepared for a kind of fluorine-containing perovskite structural material of the present invention
Figure.
Embodiment
The present invention provides a kind of perovskite structural material and preparation method thereof, application, to make the purpose of the present invention, technical side
Case and effect are clearer, clear and definite, and the present invention is described in more detail below.It should be appreciated that specific reality described herein
Example is applied only to explain the present invention, is not intended to limit the present invention.
The invention provides a kind of fluorine-containing perovskite structural material, wherein, the chemistry of the fluorine-containing perovskite structural material
Formula is RNH3MX3-aYa, wherein, R is fluoro-alkyl, and M is metallic element, and X and Y are respectively any one in Cl, Br or I, 0≤
a≦3。
Specifically, in the fluoro-alkyl, 1≤C Ge Shuo≤12, the H element on the alkyl can be complete by fluorine element
Portion or part replace, for example, when C number is 1, then the fluoro-alkyl can be CF3- or CH2F- or CHF2-；Preferably
Ground, when the number of carbon is more, and the quantity that is replaced by fluorine element of H element it is more when, the fluorine-containing perovskite structural material
Hydrophobic performance is stronger, is less susceptible to be oxidized.
Further, the compound R NH3MX3-aYaIn, X and Y can be the same element in Cl, Br, I, or
Different elements；The M is Pb2+、Ge2+、Sn2+、Cu2+、Ni2+、Co2+、Fe2+、Mn2+、Cr2+、Pd2+、Cd2+、Eu2+Or Yb2+In
One kind.
For example, the chemical formula of the fluorine-containing perovskite structural material can be CF3NH3PbI3、C2H2F4NH3PbClBr2、
C3H2F7NH3PbBr2I etc..
Based on above-mentioned fluorine-containing perovskite structural material, the present invention also provides a kind of preparation side of fluorine-containing perovskite structural material
Method, wherein, as shown in figure 1, including step：
S1, presoma preparation：Fluoro-alkyl ammonia is mixed by a certain percentage with HX and is dissolved in organic solvent, the scheduled time is stirred
Decompression screws out solvent afterwards, and drying obtains presoma；
Specifically, in the preparation process of presoma, the fluoro-alkyl is 1 with HX mol ratios：2.01-1：2.1；The HX
Can be one or more mixing in HCl, HI or HBr；The organic solvent is preferably absolute ethyl alcohol；Further, in forerunner
In the preparation process of body, mixing time is 1-3h, preferably 2h；Solvent is screwed out by decompression method after stirring, it is white by what is obtained
Color powder is washed three times with ether, is dried in vacuum overnight at 60 DEG C, that is, is obtained presoma.
S2, perovskite structural material preparation：By the presoma and MY2Mixing is dissolved in organic solvent, after stirring
To precipitation, the fluorine-containing perovskite structural material is made in the precipitation drying.
Specifically, in S2 steps, precursor and MY2Mol ratio can arbitrarily mol ratio combine, MY2Can be one
The mixing of kind or a variety of halo metals；And the preferred dimethylformamide of organic solvent in the step.
A kind of preparation method of fluorine-containing perovskite structural material of the present invention is illustrated below by a specific embodiment：
Embodiment 1
In embodiment 1, R is trifluoromethyl in fluorine-containing perovskite structural material, and its structural formula is：CF3NH3PbI3, specific system
Standby step is as follows：
The synthesis of precursor trifluoro iodine methylamine：Under ice bath, ethanol（100ml）In, add HI（12.79g, 10mmol）, stirring
Under, it is passed through trifluoro methylamine gas 30 minutes, stirs two hours, ethanol is screwed out under vacuum, obtains white powder, ether washing three
It is secondary, 60oIt is dried in vacuum overnight under C
It is prepared by perovskite material：Trifluoro iodine methylamine（2.12g, 10mmol）, PbI2（4.6g, 10mmol）It is dissolved in 50mlDMF, stirs
Mix 1 hour, DMF is instilled in 300ml ether, yellow solid is obtained, filtering is drained, and is dried in vacuum overnight, you can chemistry is made
Formula is CF3NH3PbI3Fluorine-containing perovskite structural material.
Further, the present invention is CF also to chemical formula3NH3PbI3Fluorine-containing perovskite structural material and not fluorine-containing perovskite
The stability of structural material is contrasted：
By both materials simultaneously exposed to same environmental conditions air in, by it was found that, the present invention provide it is fluorine-containing
Just there is fraction of decomposition after perovskite structural material exposure 72h；Just all divide after exposure 36h without fluorine-containing perovskite material
Solution；This result shows that fluorine-containing perovskite structural material prepared by the present invention is relative to not fluorine-containing perovskite structural material
Stability is significantly improved.
Based on above-mentioned fluorine-containing perovskite structural material, present invention also offers a kind of answering for fluorine-containing perovskite structural material
With, wherein, the light-absorption layer that the fluorine-containing perovskite structural material is used in solar cell device.
Specifically, as shown in Fig. 2 the perovskite solar cell device structure includes transparent substrates 10, transparent successively
Conductive layer 20, hole transmission layer 30, the light-absorption layer 40 prepared by fluorine-containing perovskite structural material, electron transfer layer 50, negative electrode circle
Face decorative layer 60 and metal electrode 70.
Further, the specific preparation process of the perovskite solar cell is as follows：
ITO electro-conductive glass is used under acetone, deionized water, isopropanol supersound washing, 80 ° of vacuum and dried 12 hours successively；Made on ITO
Standby NiOx films；Perovskite precursor solution is configured, is dissolved in DMSO, is spin-coated on NiOx films, 100 ° are annealed 10 minutes；Match somebody with somebody
Electron transfer layer solution is put, by PCBM solution chloroforms, concentration is 10mg/ml, is prepared by spin-coating method on perovskite thin film；
BCP and metal electrode are deposited successively.
There is the solar cell prepared by fluorine-containing perovskite structural material provided using the present invention excellent photoelectricity to turn
Efficiency is changed, and performance is stable, and service life is long.
In summary, the fluorine-containing perovskite structural material that the present invention is provided, fluorine element instead of the part hydrogen member on alkyl
Element so that the fluorine-containing perovskite structural material of preparation has stronger hydrophobic performance, and performance stable in the air is stronger, be difficult by
Oxidation, can be widely used in area of solar cell.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect scope.
Claims (10)
1. a kind of fluorine-containing perovskite structural material, it is characterised in that the chemical formula of the fluorine-containing perovskite structural material is
RNH3MX3-aYa, wherein, R is fluoro-alkyl, and M is metallic element, and X and Y are respectively any one in Cl, Br or I, 0≤a≤
3。
2. fluorine-containing perovskite structural material according to claim 1, it is characterised in that in the fluoro-alkyl, 1≤C's
Ge Shuo≤12.
3. fluorine-containing perovskite structural material according to claim 1, it is characterised in that the M is Pb2+、Ge2+、Sn2+、Cu2 +、Ni2+、Co2+、Fe2+、Mn2+、Cr2+、Pd2+、Cd2+、Eu2+Or Yb2+In one kind.
4. a kind of preparation method of fluorine-containing perovskite structural material as described in claim 1-3 is any, it is characterised in that including
Step：
The preparation of presoma：Fluoro-alkyl ammonia is mixed by a certain percentage with HX and is dissolved in organic solvent, after the stirring scheduled time
Decompression screws out solvent, and drying obtains presoma；
The preparation of perovskite structural material：By the presoma and MY2Mixing is dissolved in organic solvent, is precipitated after stirring, will
The fluorine-containing perovskite structural material is made in the precipitation drying.
5. the preparation method of fluorine-containing perovskite structural material according to claim 4, it is characterised in that in the system of presoma
During standby, the fluoro-alkyl is 1 with HX mol ratios：2.01-1：2.1.
6. the preparation method of fluorine-containing perovskite structural material according to claim 4, it is characterised in that in the system of presoma
During standby, the organic solvent is absolute ethyl alcohol.
7. the preparation method of fluorine-containing perovskite structural material according to claim 4, it is characterised in that in the system of presoma
During standby, after solvent is screwed out, obtained white powder washed three times with ether, is dried in vacuum overnight, obtains at 60 DEG C
To presoma.
8. the preparation method of fluorine-containing perovskite structural material according to claim 4, it is characterised in that in the system of presoma
During standby, mixing time is 1-3h.
9. the preparation method of fluorine-containing perovskite structural material according to claim 1, it is characterised in that in perovskite structure
In the preparation process of material, the organic solvent is dimethylformamide.
10. the application of a kind of fluorine-containing perovskite structural material as described in claim 1-3 is any, it is characterised in that described to contain
The light-absorption layer that perovskite fluorides structural material is used in solar cell device.
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| CN108649125A (en) * | 2018-06-04 | 2018-10-12 | 西北工业大学 | A method of improving perovskite material humidity stability |
| CN109957394A (en) * | 2017-12-26 | 2019-07-02 | 致晶科技（北京）有限公司 | A kind of perovskite material and its preparation method and application |
| CN110305349A (en) * | 2018-03-20 | 2019-10-08 | 致晶科技（北京）有限公司 | A kind of composite material and preparation method and application |
| CN111816772A (en) * | 2020-06-22 | 2020-10-23 | 隆基绿能科技股份有限公司 | Perovskite solar cell, production method and perovskite cell component |
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| CN110305349A (en) * | 2018-03-20 | 2019-10-08 | 致晶科技（北京）有限公司 | A kind of composite material and preparation method and application |
| CN108649125A (en) * | 2018-06-04 | 2018-10-12 | 西北工业大学 | A method of improving perovskite material humidity stability |
| CN108649125B (en) * | 2018-06-04 | 2019-09-10 | 西北工业大学 | A method of improving perovskite material humidity stability |
| CN111816772A (en) * | 2020-06-22 | 2020-10-23 | 隆基绿能科技股份有限公司 | Perovskite solar cell, production method and perovskite cell component |
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