CN109052455B - Preparation method of nontoxic stable perovskite - Google Patents

Preparation method of nontoxic stable perovskite Download PDF

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CN109052455B
CN109052455B CN201811181959.4A CN201811181959A CN109052455B CN 109052455 B CN109052455 B CN 109052455B CN 201811181959 A CN201811181959 A CN 201811181959A CN 109052455 B CN109052455 B CN 109052455B
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reaction
preparation
raw materials
precipitate
organic solvent
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CN109052455A (en
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高志强
密保秀
郑树超
石莹
徐昕
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Nanjing University of Posts and Telecommunications
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Nanjing University of Posts and Telecommunications
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G19/00Compounds of tin
    • C01G19/006Compounds containing, besides tin, two or more other elements, with the exception of oxygen or hydrogen

Abstract

The invention discloses a preparation method of a non-toxic stable perovskite, which comprises the following steps of S1, weighing reaction raw materials, putting the reaction raw materials into an organic solvent, heating for reaction, and stirring for 2-12 hours; s2, adding a cleaning solvent into the reaction product of S1, and standing for 3-5 minutes; s3, filtering the reaction product of S2, removing a solution part of the reaction product to obtain a precipitate, and then cleaning the precipitate for 3-5 times by using a cleaning solvent; and S4, placing the precipitate cleaned in the S3 into an oven to be dried for 5-8 hours, and obtaining a final product. The preparation method of the invention avoids the operation steps of adding reactants at high temperature and preparing precursor solution in the existing solution preparation method, not only simplifies the reaction process, but also avoids the special equipment requirement and the reaction atmosphere requirement in the solid reaction method.

Description

Preparation method of nontoxic stable perovskite
Technical Field
The invention relates to a preparation method of perovskite, in particular to a preparation method of nontoxic stable perovskite applied to a solar cell, and belongs to the technical field of photoelectricity.
Background
The development of perovskites has made significant efforts over the past decades, and lead-based perovskite battery devices have currently exceeded 20% efficiency. However, the toxicity of lead-based perovskite materials in the conventional art greatly restricts further commercial application thereof, and thus, research on non-toxic perovskite materials is imminent.
In recent years, Sn-based2+The perovskite is favored by researchers due to the green and non-toxic characteristic. At present, Sn-based materials have been successfully prepared2+The solar cell device of (1). FASnI-based study by Shao et al3The photoelectric conversion efficiency of the perovskite cell device can reach 9 percent. At the same time, based on Sn2+All-inorganic perovskite CsSnI3Has also been successfully applied in photovoltaic devices and has obtained a photoelectric conversion efficiency of 4.8%. Although based on Sn in contrast to lead-based perovskites2+The perovskite avoids the influence of toxicity on people to the maximum extent, but the property is more unstable, and in the air, Sn2+Is oxidized into Sn4+This greatly limits Sn2+The use of perovskites in practical production. Thus, stable against toxicityThe production, preparation and application research of the novel perovskite material become a new trend of the current development.
In the latest research, one is based on Sn4+Of perovskite material Cs2SnAxB6-x(wherein A, B is halogen, x is more than or equal to 0 and less than or equal to 6) is paid attention to, and the novel perovskite has the advantages of no toxicity, stability, narrow band gap, high absorption coefficient and the like. In the present study results, Cs2SnAxB6-xThe light absorption material has been successfully applied to a planar junction solar cell and a mesoporous perovskite cell, and the photoelectric conversion efficiency of about 1 percent is respectively obtained. Meanwhile, the research shows that Cs2SnAxB6-xThe composite material also has good hole transmission performance, and can be used as a hole transmission material to be applied to a solid dye-sensitized cell, so that the corrosion of electrolyte in a liquid dye-sensitized cell to the cell and the packaging problem caused by the existence of the liquid electrolyte are avoided. In addition, researchers have also addressed Cs2SnAxB6-xThe homologues are researched and researched, and mainly comprise that Ag, Te and the like are used for replacing Sn to synthesize related perovskite materials, and the photoelectric properties of the perovskite materials are researched and researched. The series of results show that the production, preparation and application research of the novel perovskite material have great significance for the development of a new generation of nontoxic stable solar cells.
In Cs2SnAxB6-xIn terms of production and preparation, the preparation methods reported at present mainly comprise a solid reaction method and a solution reaction method. The solid reaction method not only requires a high temperature of up to 400 ℃, but also requires special equipment to ensure a high vacuum environment or an inert gas atmosphere, which is not conducive to mass production. In the solution reaction method, Sn is generally used4+Or Sn2+Solution as Sn source (Sn)2+The solution is first oxidized to Sn4+Solution) and CsA (A is halogen) solution to generate the target product. Although the above-described procedure is not complicated, researchers have discovered, in experimental trials, the shortcomings of the above-described procedure. For example, in these preparation methods, the addition at an elevated temperature of 120 ℃ is requiredThe initial reactant or the precursor solution which needs to be prepared first for the next reaction brings great limitation to the preparation process, so the solid reaction method or the solution reaction method is not beneficial to the non-toxic and stable perovskite Cs2SnAxB6-xThe scale production and preparation of the solar cell can influence the further application of the solar cell.
In conclusion, how to provide a new nontoxic stable perovskite Cs based on the prior art2SnAxB6-xThe preparation method simplifies the reaction method as much as possible, overcomes various limiting conditions in the preparation process, and becomes a new research direction for technicians in the industry.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a preparation method of non-toxic stable perovskite,
the preparation route is as follows,
,
a, B is any halogen atom, m, n, l, x, y and z are constants more than or equal to 0, and m and n are not 0 at the same time, and l and x are not 0 at the same time;
x is any constant in the interval [0,6 ];
when x is 0, the reaction formula is,
or is or
The preparation method comprises the following steps of,
s1, weighing reaction raw materials, putting the reaction raw materials into an organic solvent, heating for reaction, and stirring for 2-12 hours;
s2, adding a cleaning solvent into the reaction product of S1, and standing for 3-5 minutes;
s3, filtering the reaction product of S2, removing a solution part of the reaction product to obtain a precipitate, and then cleaning the precipitate for 3-5 times by using a cleaning solvent;
and S4, placing the precipitate cleaned in the S3 into an oven to be dried for 5-8 hours, and obtaining a final product.
Preferably, in S1, after the reaction raw materials are weighed, the reaction raw materials are dissolved in the organic solvent, respectively, and then mixed and heated for reaction.
Preferably, in S1, after the reaction raw materials are weighed, any two or more of the reaction raw materials are mixed, followed by dissolving in an organic solvent and heating for reaction.
Preferably, the organic solvent in S1 is 1, 4-butyrolactone.
Preferably, in the step S1, the reaction raw materials are put into an organic solvent for heating reaction, and the reaction temperature is 25 to 220 ℃.
Preferably, the reaction raw materials are put into the organic solvent for heating reaction in S1, and the reaction temperature is 70 ℃.
Preferably, the cleaning solvent described in S2 and S3 is an alcohol organic solvent.
Preferably, the cleaning solvent described in S2 and S3 is ethanol.
Compared with the prior art, the invention has the advantages that:
cs provided by the invention2SnAxB6-xThe novel solution preparation method of (A, B is halogen) avoids the operation steps of adding reactants at high temperature and preparing precursor solution in the existing solution preparation method, not only simplifies the reaction process, but also avoids the special equipment requirement and reaction atmosphere requirement in the solid reaction method, the whole operation of the preparation method is simple, and the preparation method can be directly applied to the process of large-scale production and preparation and has huge potential application value.
In addition, the invention also provides reference for other related problems in the same field, can be expanded and extended on the basis of the reference, is applied to technical schemes of other preparation methods in the same field, and has very wide application prospect.
The following detailed description of the embodiments of the present invention is provided in connection with the accompanying drawings for the purpose of facilitating understanding and understanding of the technical solutions of the present invention.
Drawings
FIG. 1 shows Cs prepared in example 1 of the present invention using 1, 4-butyrolactone (GBL) and N, N-dimethylformamide as reaction solvents, respectively2SnI6XRD characterization pattern of (a);
FIG. 2 is an EDS characterization of Cs2SnI6 prepared using GBL as a solvent in example 1 of the present invention;
FIG. 3 is an XRD characterization of Cs2SnBr6 prepared in example 2 of the present invention;
fig. 4 is an XRD characterization of Cs2SnBr3I3 prepared in example 3 of the present invention.
Detailed Description
The invention discloses a preparation method of nontoxic stable perovskite,
the preparation route is as follows,
a, B is any halogen atom, M, N, L, X, y and z are any constant more than or equal to 0, M and N are not 0 at the same time, and L and X are not 0 at the same time; x is any constant between 0 and 6, and comprises two constants of 0 and 6. In particular, when x is 0, the reaction formula is:
,
or
,
The preparation method comprises the following steps of,
s1, weighing the reaction raw materials, putting the reaction raw materials into an organic solvent, heating for reaction, and stirring for 2-12 hours. The organic solvent is 1, 4-butyrolactone (GBL), with which very pure target products can be obtained. The reaction temperature is 25-220 ℃, and in the present embodiment, the preferable reaction temperature is 70 ℃.
S2, adding a cleaning solvent into the reaction product of S1, and standing for 3-5 minutes.
S3, filtering the reaction product of S2, removing a solution part of the reaction product to obtain a precipitate, and then cleaning the precipitate for 3-5 times by using a cleaning solvent. The cleaning solvent is an alcohol organic solvent, and in this embodiment, ethanol is preferred.
And S4, placing the precipitate cleaned in the S3 into an oven to be dried for 5-8 hours, and obtaining a final product.
In S1, after weighing the reaction materials, there are two operation modes, one of which is that the reaction materials are dissolved in the organic solvent, and then mixed and heated to react. Secondly, any two or more of the reaction raw materials may be mixed, and then dissolved in an organic solvent and heated for reaction.
The above technical solution is specifically described below with reference to specific examples.
Example 1: cs2SnI6Synthesis of (2)
1.036g CsI and 0.744g SnI were weighed out separately20.508g of I25ml of organic solvent 1, 4-butyrolactone (GBL) or N, N-Dimethylformamide (DMF) are taken and added into a 10 ml reaction bottle containing magnetons in turn to form a mixed solution. And (3) placing the mixed solution on a magnetic hot plate, stirring and reacting at 70 ℃, stopping the reaction after 10 hours, adding absolute ethyl alcohol into a reaction bottle, standing for 3-5 minutes, removing part of the upper solution in the reaction bottle to obtain a black precipitate, then washing the precipitate for 3-5 times by using the absolute ethyl alcohol, and after the washing is finished, placing the precipitate in an oven to be dried for 5-8 hours at 70 ℃ to obtain a final product. FIG. 1 is a representation of XRD test of the product obtained using GBL and DMF as reaction solventsMiddle dotted line is simulated Cs2SnI6And (4) data. When GBL is used as a reaction solvent, XRD diffraction peaks and simulated Cs of the product2SnI6Data peaks are completely overlapped, and no impurity peak exists; when DMF is used as a reaction solvent, diffraction peaks of CsI appear in an XRD test characterization diagram of the obtained product, namely CsI impurities appear in the product. FIG. 2 is a graph showing the EDS test characterization of the product obtained using GBL as the reaction solvent, in which the ratio of the number of atoms of the product Cs: Sn: I =20.98:12.75:66.27 substantially corresponds to Cs2SnI6The atomic number ratio in (A) proves that the product has high purity.
Example 2: cs2SnBr6Synthesis of
0.85g CsBr and 1.11g SnBr were weighed out separately25ml of 1, 4-butyrolactone, an organic solvent, was weighed out and sequentially added to a 10 ml reaction flask containing magnetons to form a mixed solution. And (3) placing the mixed solution on a magnetic hot plate, stirring and reacting at 70 ℃, stopping the reaction after 10 hours, adding absolute ethyl alcohol into a reaction bottle, standing for 3-5 minutes, removing part of the solution at the middle upper part of the reaction bottle to obtain a precipitate, then washing the precipitate for 3-5 times by using the absolute ethyl alcohol, and after the washing is finished, placing the precipitate in an oven, and drying for 5-8 hours at 70 ℃ to obtain a final product. FIG. 3 is a XRD test characterization of the product with simulated Cs in the dotted line2SnBr6Data, product XRD diffraction peaks and simulated Cs2SnBr6The data peaks coincide. The above results show that when CsBr and SnBr were used2When the GBL is a reaction solvent as a reaction raw material, the target product Cs can be obtained2SnBr6
Example 3: cs2SnBr3I3Synthesis of
0.1170 g CsI and 0.1007 g SnI are weighed out respectively20.0376 g of SnBr20.5 ml of 1, 4-butyrolactone, an organic solvent, was weighed out and sequentially added to a 5ml reaction flask containing magnetons to form a mixed solution. Placing the mixed solution on a magnetic hot plate, stirring at 70 deg.C for reaction, stopping reaction after 10 hr, adding anhydrous ethanol into the reaction flask, standing for 3-5 min, removing the upper part of the solution to obtain precipitate, and allowing the precipitate to reactWashing the precipitate with anhydrous ethanol for 3-5 times, and drying the precipitate in an oven at 70 deg.C for 5-8 hr to obtain the final product. FIG. 4 is a XRD test characterization of the product with simulated Cs in the dotted line2SnBr3I3Data, product XRD diffraction peaks and simulated Cs2SnBr3I3The data peaks coincide. The above results show that when CsI, SnI are used in a certain ratio2And SnBr2When the GBL is a reaction solvent as a reaction raw material, the target product Cs can be obtained2SnBr3I3
Cs provided by the invention2SnAxB6-xThe novel solution preparation method (A, B is halogen, x is more than or equal to 0 and less than or equal to 6) avoids the operation steps of adding reactants and preparing precursor solution at high temperature in the existing solution preparation method, not only simplifies the reaction process, but also avoids the special equipment requirement and reaction atmosphere requirement in the solid reaction method, the whole preparation method is simple to operate, can be directly applied to the process of large-scale production and preparation, and has huge potential application value.
In addition, the invention also provides reference for other related problems in the same field, can be expanded and extended on the basis of the reference, is applied to technical schemes of other preparation methods in the same field, and has very wide application prospect.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein, and any reference signs in the claims are not intended to be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (3)

1. A preparation method of nontoxic and stable perovskite is characterized by comprising the following steps:
the preparation route is as follows,
a, B is any halogen atom, m, n, l, x, y and z are constants more than or equal to 0, and m and n are not 0 at the same time, and l and x are not 0 at the same time;
x is any constant in the interval [0,6 ];
when x is 0, the reaction formula is,
the preparation method comprises the following steps of,
s1, weighing reaction raw materials, putting the reaction raw materials into an organic solvent, heating for reaction, and stirring for 2-12 hours;
s2, adding a cleaning solvent into the reaction product of S1, and standing for 3-5 minutes;
s3, filtering the reaction product of S2, removing a solution part of the reaction product to obtain a precipitate, and then cleaning the precipitate for 3-5 times by using a cleaning solvent;
s4, placing the cleaned precipitate in the S3 and drying the precipitate in an oven for 5-8 hours to obtain a final product;
in S1, after weighing the reaction raw materials, respectively dissolving the reaction raw materials in an organic solvent, then mixing and heating for reaction;
in S1, after the reaction raw materials are weighed, any two or more of the reaction raw materials are mixed, followed by dissolving in an organic solvent and heating for reaction.
The organic solvent in S1 is 1, 4-butyrolactone;
in S1, the reaction raw materials are put into an organic solvent for heating reaction, and the reaction temperature is 25-220 ℃;
in S1, the reaction raw materials are put into an organic solvent for heating reaction, and the reaction temperature is 70 ℃.
2. A method according to claim 1 for the preparation of a non-toxic stable perovskite, wherein: the cleaning solvent described in S2 and S3 is an alcohol organic solvent.
3. A method according to claim 1 for the preparation of a non-toxic stable perovskite, wherein: the cleaning solvent described in S2 and S3 is ethanol.
CN201811181959.4A 2018-10-11 2018-10-11 Preparation method of nontoxic stable perovskite Active CN109052455B (en)

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GB201414110D0 (en) * 2014-08-08 2014-09-24 Isis Innovation Thin film production
US9334443B1 (en) * 2014-10-31 2016-05-10 Sun Harmonics, Ltd. Synthesis of CsSnI3 by a solution based method
CN104934304B (en) * 2015-06-04 2018-04-27 苏州大学 A kind of method that mixed solvent induction regulating controlling by under room temperature obtains black cubic system perovskite thin film
CN105733574B (en) * 2016-01-31 2018-06-12 南京理工大学 A kind of method that low temperature solution polycondensation prepares perovskite quantum dot
CN107934916B (en) * 2017-11-16 2020-10-20 中山大学 Preparation method of stable lead-free all-inorganic double perovskite A2 BB' X6 nanocrystal
CN108389969B (en) * 2018-03-01 2021-08-13 广东工业大学 Green solvent system and mixed solution for preparing perovskite layer of perovskite solar cell

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