CN115521210A - Perovskite material and preparation method and application thereof - Google Patents
Perovskite material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 114
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 35
- ADNPLDHMAVUMIW-CUZNLEPHSA-N substance P Chemical compound C([C@@H](C(=O)NCC(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CCSC)C(N)=O)NC(=O)[C@H](CC=1C=CC=CC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@@H](N)CCCN=C(N)N)C1=CC=CC=C1 ADNPLDHMAVUMIW-CUZNLEPHSA-N 0.000 claims abstract description 16
- 238000003746 solid phase reaction Methods 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims description 83
- 238000010438 heat treatment Methods 0.000 claims description 66
- 239000000243 solution Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 28
- LLWRXQXPJMPHLR-UHFFFAOYSA-N methylazanium;iodide Chemical compound [I-].[NH3+]C LLWRXQXPJMPHLR-UHFFFAOYSA-N 0.000 claims description 22
- 238000000746 purification Methods 0.000 claims description 20
- 239000000376 reactant Substances 0.000 claims description 16
- QHJPGANWSLEMTI-UHFFFAOYSA-N aminomethylideneazanium;iodide Chemical compound I.NC=N QHJPGANWSLEMTI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 12
- JMXLWMIFDJCGBV-UHFFFAOYSA-N n-methylmethanamine;hydroiodide Chemical compound [I-].C[NH2+]C JMXLWMIFDJCGBV-UHFFFAOYSA-N 0.000 claims description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- -1 amine cation Chemical class 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 4
- UPHCENSIMPJEIS-UHFFFAOYSA-N 2-phenylethylazanium;iodide Chemical compound [I-].[NH3+]CCC1=CC=CC=C1 UPHCENSIMPJEIS-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940107816 ammonium iodide Drugs 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- CALQKRVFTWDYDG-UHFFFAOYSA-N butan-1-amine;hydroiodide Chemical compound [I-].CCCC[NH3+] CALQKRVFTWDYDG-UHFFFAOYSA-N 0.000 claims description 4
- UUDRLGYROXTISK-UHFFFAOYSA-N carbamimidoylazanium;iodide Chemical compound I.NC(N)=N UUDRLGYROXTISK-UHFFFAOYSA-N 0.000 claims description 4
- XFYICZOIWSBQSK-UHFFFAOYSA-N ethylazanium;iodide Chemical compound [I-].CC[NH3+] XFYICZOIWSBQSK-UHFFFAOYSA-N 0.000 claims description 4
- ZZLONYJSCSHJMR-UHFFFAOYSA-N hydron 2,2,2-trifluoroethanamine iodide Chemical compound [I-].FC(C[NH3+])(F)F ZZLONYJSCSHJMR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- ISWNAMNOYHCTSB-UHFFFAOYSA-N methanamine;hydrobromide Chemical compound [Br-].[NH3+]C ISWNAMNOYHCTSB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 3
- 150000004820 halides Chemical group 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- XQPRBTXUXXVTKB-UHFFFAOYSA-M caesium iodide Chemical compound [I-].[Cs+] XQPRBTXUXXVTKB-UHFFFAOYSA-M 0.000 claims description 2
- 229940046892 lead acetate Drugs 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000002441 X-ray diffraction Methods 0.000 description 45
- 239000000843 powder Substances 0.000 description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 239000001257 hydrogen Substances 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 18
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229940071870 hydroiodic acid Drugs 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 238000000133 mechanosynthesis reaction Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/03—Monoamines
- C07C211/04—Mono-, di- or tri-methylamine
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/03—Monoamines
- C07C211/07—Monoamines containing one, two or three alkyl groups, each having the same number of carbon atoms in excess of three
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/02—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C211/15—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
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- C07C211/01—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms
- C07C211/26—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring
- C07C211/27—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing at least one six-membered aromatic ring having amino groups linked to the six-membered aromatic ring by saturated carbon chains
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
- C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
- C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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Abstract
The invention discloses a perovskite material and a preparation method and application thereof. The preparation method of the perovskite material comprises the following steps: carrying out solid-phase reaction on the substance m, the substance p and the substance n; the substance m is one or more AX; substance p is one or more DXs; the substance n is one or more BY 2 . The preparation method of the perovskite material is simple, low in equipment requirement, low in energy consumption, environment-friendly, low in raw material cost, high in atom economy and reaction efficiency, and beneficial to industrial production.
Description
Technical Field
The invention relates to the field of material science and technology and photoelectric application, in particular to a perovskite material and a preparation method and application thereof.
Background
Perovskite materials are widely applied to semiconductor photoelectric devices, such as solar cells, photodetectors, light emitting diodes, high-energy ray scintillators, field effect transistors, memristors and other fields, due to the advantages of controllable direct band gaps, high electron mobility, high absorption coefficients, long carrier life and the like. Compared with the traditional silicon-based semiconductor material, the perovskite material has low production cost, wide raw material source and low production cost; moreover, the material has excellent optoelectronic properties, such as low defect density, high carrier mobility, ultra-long carrier diffusion distance, high defect tolerance, and the like.
At present, the organic metal halide perovskite is developed very rapidly in the field of solar cells, and the photoelectric conversion efficiency of the prepared solar cells is developed rapidly and reaches a very high level, which is increased to 25.5% rapidly from 3.8% in 2009 to 2020.
At present, the preparation method of the film in the device is mainly a solution method or a deposition method, although the purity of the obtained material is high, the two methods have complex process conditions, high equipment requirements and high energy consumption, and the solvent has large pollution to the environment and is not environment-friendly.
Literature (Prochowicz D, yadav P, saliba M, et al, mechanosynthesis of pure phase mixed-location MA x FA1 x PbI 3 hybrid perovskites:photovoltaic performance and electrochemical properties[J].Sustainable Energy&Fuels,2017, 1.) discloses the use of methylamine hydroiodide (MAI), formamidine hydroiodide (FAI) and lead iodide (PbI) 2 ) A method for solid-phase synthesis of perovskite. Although the method has simple process, the raw material cost is higher and the reaction efficiency is lower.
Therefore, it is urgently needed to provide a preparation method of perovskite material with simple process, environmental protection, low raw material cost and high reaction efficiency.
Disclosure of Invention
The invention aims to provide a perovskite material, a preparation method and application thereof and a solar cell. The preparation method of the perovskite material is simple, low in equipment requirement, low in energy consumption, environment-friendly, low in raw material cost, high in atom economy and reaction efficiency, and beneficial to industrial production.
The inventor shows through experiments that: selecting raw materials AX and BY 2 Then AX +2DX + BY can occur 2 ＝ABX 3 +2DY or 2AX +2DX + BY 2 ＝A 2 BX 4 +2DY in a solid phase; wherein, ABX 3 And A 2 BX 4 Is the target product perovskite material. And when the byproduct DY is the ionic liquid, the method is green and environment-friendly and can be further recycled. The perovskite material with high purity and good thermal stability can be prepared by the specially selected raw materials and the preparation method, and the perovskite material is used in the solar cell and has high conversion efficiency.
In order to achieve the above object, the present invention provides the following technical solutions:
one of the technical schemes provided by the invention is as follows: a method of preparing a perovskite material, comprising the steps of: carrying out solid-phase reaction on the substance m, the substance p and the substance n;
the substance m is one or more AX; the substance p is one or more DXs; the substance n is one or more BY 2 ；
Wherein A is independently Cs + Or an organic amine cation;
d is independently an organic amine cation, NH 4 + 、K + Or Na + ；
Said X is independently a halide;
said B is independently Pb 2+ 、Sn 2+ 、Ge 2+ 、Cu 2+ 、Mn 2+ 、Fe 2+ 、Bi 3+ 、Tb 3+ Or Zn 2+ ；
Y is independently CH 3 COO - 、C 2 O 4 2- 、CF 3 COO - 、CH 3 CHOHCOO - 、HCOO - 、CF 3 SO 3 - 、BF 4 - Or PF 6 - 。
In the present invention, (the amount of substance of the substance m + the amount of substance of the substance p): (amount of substance n) may be (1 to 8): 1; preferably (2 to 5): 1; more preferably (3 to 4): 1.
the molar ratio of the substance m, the substance p and the substance n may be (1 to 4): (1-4): 1; preferably 1.
In the present invention, the substance m is preferably one or two kinds of AX.
Wherein when the substance m is two AXs, the mass ratio of the two AXs can be (0.1-10): 1, preferably (0.2 to 2): 1 or (8 to 9): 1.
the substance p is preferably one or two DXs.
Wherein when the substance p is two DXs, the mass ratio of the two DXs can be (0.1-10): 1, more preferably (0.2 to 2): 1 or (8 to 9): 1.
the substance n is preferably one or two Bys 2 。
In the present invention, the organic amine cation is preferably CH 3 NH 3 + 、HC(NH 2 ) 2 + 、CH 3 CH 2 NH 3 + 、CH 3 (CH 2 ) 2 NH 3 + 、CH 3 (CH 2 ) 3 NH 3 + 、CF 3 CH 2 NH 3 + 、(CH 3 ) 2 NH 2 + 、C(NH 2 ) 3 + Or
Such as CH 3 NH 3 + 、(CH 3 ) 2 NH 2 + 、CH 3 NH 3 + Or HC (NH) 2 ) 2 + 。
D is preferably NH 4 + 、K + Or Na + 。
The halide ion may be conventional in the art, and is preferably I - 、Br - Or Cl - (ii) a For example I - Or Br - 。
Said B is independently preferably Pb 2+ 、Sn 2+ 、Ge 2+ Or Cu 2+ (ii) a More preferably Pb 2+ Or Sn 2+ 。
Said Y is independently preferably HCOO - Or CH 3 COO - (ii) a More preferably CH 3 COO - 。
In the present invention, the AX is preferably one or more of cesium iodide, methylamine hydrobromide, methylamine hydroiodide, ethylamine hydroiodide, phenethylamine hydroiodide, trifluoroethylamine hydroiodide, butylamine hydroiodide, dimethylamine hydroiodide, formamidine hydroiodide and guanidine hydroiodide; more preferred are methylamine hydroiodide and dimethylamine hydroiodide, or formamidine hydroiodide and methylamine hydroiodide.
The DX is preferably one or more of methylamine hydrobromide, methylamine hydroiodide, ethylamine hydroiodide, phenethylamine hydroiodide, trifluoroethylamine hydroiodide, butylamine hydroiodide, dimethylamine hydroiodide, formamidine hydroiodide, guanidine hydroiodide, sodium iodide, potassium bromide and ammonium iodide; more preferred are sodium iodide, potassium bromide, ammonium iodide, methylamine hydroiodide and dimethylamine hydroiodide, or formamidine hydroiodide and methylamine hydroiodide.
Wherein, when the AX or DX is methylamine hydroiodide and dimethylamine hydroiodide, the mass ratio of the methylamine hydroiodide to the dimethylamine hydroiodide can be (8-9): 1; preferably 8.27:1.
when the AX or the DX is formamidine hydroiodide and methylamine hydroiodide, the mass ratio of the formamidine hydroiodide to the methylamine hydroiodide may be (0.2 to 2): 1; preferably 1.08: 1. 0.36: 1. 0.72:1 or 1.62:1.
the BY 2 Preferably lead acetate and/or tin acetate.
The BY 2 Crystal water or adsorbed water may be present.
In the present invention, the perovskite material preferably has a molecular formula of ABX 3 And/or A 2 BX 4 (ii) a Wherein said A, said X and said B are as previously described. The ABX 3 Can be MAPbI 3 、MAPbBr 3 、FAPbI 3 、MA 0.9 DMA 0.1 PbI 3 、FA 0.5 MA 0.5 PbI 3 、FA 0.25 MA 0.75 PbI 3 、FA 0.4 MA 0.6 PbI 3 、FA 0.6 MA 0.4 PbI 3 、MAPb 0.5 Sn 0.5 I 3 、EAPbI 3 、GAPbI 3 Or TFEAPbI 3 . A is described 2 BX 4 May be BA 2 PbI 4 Or PEA 2 PbI 4 。
In the present invention, the solid phase reaction may be conventional in the art, such as milling.
Wherein, the grinding method can be manual grinding or mechanical grinding. The manually ground container can be a mortar. The diameter of the mortar may be conventional in the art, for example, 10 to 20cm. The mechanically milled container may be a ball mill.
The temperature of the milling may be conventional in the art, for example from 20 to 30 ℃, preferably 25 ℃.
The ambient conditions for the milling may be conventional in the art, such as air, a vacuum environment, or an inert atmosphere.
The method for judging the end of grinding can be conventional in the art, and generally, grinding is finished when the colors of raw materials and reactants of the solid-phase reaction are changed remarkably. For example, when AX, DX and BY 2 When the color of the reactant is white, the color of the reactant is changed from white to orange or black by grinding, and the grinding is finished. The grinding time can be 10-60 min; preferably 30-60 min; for example 35min, 40min, 45min or 50min.
In the present invention, after the solid phase reaction, optionally, a washing and/or drying step may be further included.
The method of washing may be conventional in the art, such as filtration washing or centrifugation washing; for separating the by-products of the reactants of the solid phase reaction. The filtration wash may be conventional in the art, and typically refers to the reaction of AX and BY 2 The reactant of (2) is placed in a funnel, and washing liquid is added; the funnel is preferably a buchner funnel or a sand core funnel. The centrifugal washing may be conventional in the art. The spin rate of the centrifugal washing may be conventional in the art, for example 3000 to 6000rpm, preferably 4000rpm. The time for each centrifugal washing can be 5-15 min, preferably 10min.
The washing liquid for washing may be conventional in the art, and is preferably an organic solvent. The organic solvent can be one or more of methanol, ethanol, isopropanol, acetonitrile, anisole, tetrahydrofuran, acetone, n-butanol, tert-butanol, sec-butanol, ethyl acetate, cyclohexane and toluene; preferably acetonitrile, isopropanol or ethyl acetate.
The number of washes may be conventional in the art, e.g., 1 to 4; preferably 3 times.
The volume of the wash solution may be conventional in the art, for example the volume of wash solution per 1g of reactant may be 2 to 5mL, preferably 3mL or 4mL per wash. For example, when the mass of the reactant is 6g, the volume of the acidic solution is 12 to 30mL.
After the washing, the solid and liquid can be collected separately.
In the present invention, when the solid phase reaction includes the steps of washing and drying, the drying may be drying the solid collected after washing to obtain the perovskite material.
After the solid-phase reaction, when the step of washing is not included, the drying may be to dry the reactant after the solid-phase reaction, and the perovskite material is obtained after volatilization of DY.
Wherein the drying method may be conventional in the art.
The ambient conditions for drying may be conventional in the art, such as air, vacuum environment, or inert atmosphere; preferably a vacuum environment.
The temperature of the drying may be conventional in the art, for example, 20 to 100 ℃; preferably 50-80 ℃; more preferably 60 deg.c.
The drying time may be conventional in the art, e.g. 4 to 12 hours; preferably 8h.
The drying equipment may be conventional in the art, such as a vacuum oven.
The dried perovskite material may be conventional in the art and is preferably stored hermetically. The conditions for the sealed preservation may be preservation in an inert atmosphere, preferably a nitrogen atmosphere.
In the present invention, after the washing, it is preferable to further include a step of distilling or extracting the liquid collected after the washing, for recovering the by-product and the washing liquid.
The method of distillation may be a distillation concentration method that is conventional in the art.
The equipment for the distillation may be conventional in the art, for example a rotary evaporator.
The temperature of the distillation may be conventional in the art, for example 30 to 50 ℃; preferably 35 to 45 deg.c.
The method of extraction may be conventional in the art.
In the present invention, the method for preparing the perovskite material preferably comprises the following steps: carrying out solid-phase reaction on the substance m, the substance p and the substance n to obtain a reactant; washing the reactant, and respectively collecting solid and liquid; drying the solid to obtain a perovskite material; the liquid was distilled and the washing liquid and by-product were collected separately.
In the present invention, the perovskite material may be one or more of a one-dimensional perovskite, a two-dimensional perovskite and a three-dimensional perovskite; such as a two-dimensional perovskite or a three-dimensional perovskite.
The particle size of the perovskite material may be conventional in the art, preferably in the range 3 to 6mm, for example 4 to 5mm.
The second technical scheme provided by the invention is as follows: a method of purifying a perovskite material, comprising the steps of:
heating the supersaturated solution of the perovskite material in a sectional manner to obtain the perovskite single crystal material;
wherein the staged heating comprises a first heating stage, a second heating stage and a third heating stage; the temperature difference between the first heating section and the second heating section is 10-50 ℃; the temperature difference between the second heating section and the third heating section is 10-50 ℃.
In the present invention, the perovskite material is preferably produced by the above-mentioned method for producing a perovskite material.
In the present invention, the perovskite material may be conventional in the art, e.g., MAPbI 3 、MAPbBr 3 、FAPbI 3 、MA 0.9 DMA 0.1 PbI 3 、FA 0.5 MA 0.5 PbI 3 、FA 0.25 MA 0.75 PbI 3 、FA 0.4 MA 0.6 PbI 3 、FA 0.6 MA 0.4 PbI 3 、MAPb 0.5 Sn 0.5 I 3 、EAPbI 3 、GAPbI 3 、TFEAPbI 3 、BA 2 PbI 4 Or PEA 2 PbI 4 。
In the present invention, the supersaturated solution of the perovskite material may be obtained by mixing the perovskite material with a purification solvent. The purification solvent may be conventional in the art, and is preferably one or more of aqueous hydroiodic acid, aqueous hydrobromic acid, N-dimethylformamide, dimethylsulfoxide and γ -butyrolactone.
In the present invention, the temperature of the supersaturated solution of perovskite material may be conventional in the art, typically below the boiling point of the purification solvent; for example 40 to 140 ℃.
In the present invention, preferably, the supersaturated solution of the perovskite material is transported upward through a transport pipe and then heated in stages.
Wherein the diameter of the delivery conduit may be determined according to the volume of the solution as is conventional in the art. For example, when the volume of the solution of the perovskite material is 1L, the diameter of the conveying pipeline is 1-10 cm; preferably 5cm.
The conveying speed can be 5-30 mL/min; preferably 10 to 20mL/min.
In the present invention, the temperatures of the first heating section, the second heating section, and the third heating section are preferably sequentially decreased or sequentially increased. For example, the temperatures of the first heating section, the second heating section and the third heating section are 90 ℃, 60 ℃ and 30 ℃ respectively; or, 100 deg.C, 80 deg.C, 60 deg.C; or, 90 deg.C, 100 deg.C, 110 deg.C; alternatively, 45 deg.C, 55 deg.C, 65 deg.C.
Wherein, when the purification solvent is an aqueous solution of hydroiodic acid or an aqueous solution of hydrobromic acid, the pH of the supersaturated solution of the perovskite material is 7 or less, and the temperatures of the first heating section, the second heating section and the third heating section are preferably decreased in this order.
In the present invention, after the step of heating the supersaturated solution of the perovskite material, the step of collecting the perovskite single crystal material is preferably further included.
In the invention, preferably, the purification device adopted by the purification method comprises a feeding area, a seed crystal area, a heating unit, a segmented temperature control crystal growth area, a crystal collecting area and a feed liquid circulating and returning area;
the feeding region is connected with the seed crystal region and is used for adding a solution of perovskite material into the seed crystal region;
the heating unit is used for heating the solution of the perovskite material in the seed crystal region;
the segmented temperature control crystal growth area comprises a feed liquid conveying power part and a conveying pipeline; the feed liquid conveying power component is arranged inside the conveying pipeline; one end of the conveying pipeline is positioned in the seed crystal region, and the other end of the conveying pipeline is connected with the crystal collecting region;
the conveying pipeline sequentially comprises a feed liquid conveying power part, a first heating element, a second heating element and a third heating element along the solution flowing direction of the perovskite material; the conveying pipeline is used for circulating and heating the solution of the perovskite material input from the seed crystal area;
one end of the feed liquid circulation return area is connected with the crystal collecting area and used for receiving the residual feed liquid after the perovskite single crystal material is collected in the crystal collecting area; the other end of the liquid pipe is connected with the seed crystal area and used for conveying the residual feed liquid to the seed crystal area. The perovskite material and the purification solvent can be fully utilized, and the perovskite single crystal material can be grown through multiple circulation.
The third technical scheme provided by the invention is as follows: a perovskite single crystal material is prepared by the purification method of the perovskite material.
In the invention, the molecular formula of the perovskite single crystal material is preferably ABX 3 And/or A 2 BX 4 (ii) a Wherein said A, said X and said B are as previously described.
The ABX 3 Preferably MAPbI 3 、MAPbBr 3 、FAPbI 3 、MA 0.9 DMA 0.1 PbI 3 、FA 0.5 MA 0.5 PbI 3 、FA 0.25 MA 0.75 PbI 3 、FA 0.4 MA 0.6 PbI 3 、FA 0.6 MA 0.4 PbI 3 、MAPb 0.5 Sn 0.5 I 3 、EAPbI 3 、GAPbI 3 Or TFEAPbI 3 . A is described 2 BX 4 Preferably BA 2 PbI 4 Or PEA 2 PbI 4 。
The perovskite single crystal material can be one or more of one-dimensional perovskite, two-dimensional perovskite and three-dimensional perovskite; preferably a two-dimensional perovskite or a three-dimensional perovskite.
The particle size of the perovskite single crystal material may be conventional in the art, preferably 1 to 10mm, more preferably 3 to 6mm, for example 4 to 5mm.
The fourth technical scheme provided by the invention is as follows: use of a perovskite single crystal material as hereinbefore described in a solar cell.
The fifth technical scheme provided by the invention is as follows: a solar cell comprising a perovskite single crystal material as hereinbefore described.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) The preparation method disclosed by the invention is simple, low in equipment requirement, low in energy consumption, environment-friendly, low in raw material cost, high in atom economy and reaction efficiency, and beneficial to industrial production.
(2) The preparation method can recycle the washing liquid and the byproducts, and is economical and environment-friendly.
(3) The perovskite material has low defect density, high purity and good thermal stability; when the catalyst is used in a solar cell, the conversion efficiency is high.
Drawings
FIG. 1 is a photograph of the perovskite powder of example 1;
FIG. 2 is a photograph (grid scale 1 mm) of a perovskite single crystal in example 15;
FIG. 3 is a Scanning Electron Micrograph (SEM) of the perovskite powder of example 1;
FIG. 4 is an X-ray diffraction pattern (XRD) of the perovskite powder of example 3;
FIG. 5 is an X-ray diffraction pattern (XRD) of the perovskite powder of example 1 and the perovskite single crystal of example 15;
FIG. 6 is an X-ray diffraction pattern (XRD) of the perovskite powder of example 2 and the perovskite single crystal of example 16;
FIG. 7 is an X-ray diffraction pattern (XRD) of the perovskite single crystal of example 20;
FIG. 8 is an X-ray diffraction pattern (XRD) of the perovskite single crystal of example 19;
FIG. 9 is an X-ray diffraction pattern (XRD) of the perovskite powder of example 4 and the perovskite single crystal of example 18;
FIG. 10 is an X-ray diffraction pattern (XRD) of the perovskite single crystal of example 24;
FIG. 11 is an X-ray diffraction pattern (XRD) of the perovskite single crystal of example 21;
FIG. 12 is an X-ray diffraction pattern (XRD) of the perovskite single crystal of example 22;
FIG. 13 is a 400MHz nuclear magnetic hydrogen spectrum of the perovskite powder of example 6: ( 1 H NMR)；
FIG. 14-a is the 400MHz nuclear magnetic hydrogen spectrum of the perovskite powder of example 4 ( 1 H NMR)；
FIG. 14-b is a graph comparing the nuclear magnetic hydrogen spectra of the perovskite powder of example 4 and the perovskite single crystal material of example 18;
FIG. 15 is the 400MHz nuclear magnetic hydrogen spectrum of the perovskite powder of example 8 ( 1 H NMR)；
FIG. 16 is a 400MHz nuclear magnetic hydrogen spectrum of the perovskite powder of example 7: ( 1 H NMR)；
FIG. 17 is the 400MHz nuclear magnetic hydrogen spectrum of the perovskite powder of example 3 ( 1 H NMR)；
FIG. 18 is a 400MHz nuclear magnetic hydrogen spectrum of the perovskite powder of example 1 ( 1 H NMR)；
FIG. 19 is a TGA profile of the perovskite powder of example 4 and the perovskite single crystal material of example 18;
FIG. 20 is a schematic view of an apparatus used in the purification process of perovskite materials in examples 15 to 28.
Description of the reference numerals
Feeding zone 1
Segmented temperature controlled crystal growth zone 3
Feed liquid conveying power part 31
A crystal collecting region 4
Feed liquid recycle return zone 5
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. Experimental procedures without specifying specific conditions in the following examples were selected in accordance with conventional procedures and conditions, or in accordance with commercial instructions.
Examples 1-14 preparation of perovskite materials
Grinding the raw material of the perovskite material to obtain a reactant; wherein, the container for grinding is a mortar, and the diameter of the mortar in the embodiments 1 to 11 is 10cm; the diameter of the mortar in examples 12 to 14 was 20cm;
placing the reactant in a Buchner funnel, filtering and washing the reactant for 3 times, adding a washing solution to immerse the reactant, and respectively collecting solid and liquid;
drying the solid in sequence to obtain the perovskite material
Wherein, the raw materials of the perovskite material are shown in the following table 1; the process conditions are shown in table 2 below; the reaction equation and the mass of the perovskite material are shown in table 3 below; the recovered organic solvent and by-products are shown in table 4 below.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
Examples 15-28 purification of perovskite Material
The perovskite materials prepared in examples 1 to 14 were purified, and as shown in fig. 20, the purification apparatus included a feed zone 1, a seed crystal zone 2, a heating unit 6, a segmented temperature-controlled crystal growth zone 3, a crystal collection zone 4, and a feed liquid circulation return zone 5;
the feeding region 1 is connected with the seed crystal region 2 and is used for adding a solution of perovskite material into the seed crystal region 2;
the heating unit 6 is used for heating the solution of the perovskite material in the seed crystal region 2;
the segmented temperature-controlled crystal growth region 3 comprises a feed liquid conveying power part 31 and a conveying pipeline 35; the feed liquid conveying power component 31 is a propeller and is arranged inside the conveying pipeline 35; one end of the conveying pipeline 35 is positioned in the seed crystal area 2, and the other end is connected with the crystal collecting area 4;
the crystal collecting region 4 includes a screen 41;
the volume of the perovskite material solution in the seed crystal region 2 is 1L, and the diameter of the conveying pipeline 35 is 5cm;
the conveying pipeline 35 comprises a feed liquid conveying power part 31, a first heating element 32, a second heating element 33 and a third heating element 34 in sequence along the flow direction of the solution of the perovskite material; the delivery pipe 35 is used for circulating and heating the solution of the perovskite material input from the seed crystal zone 2;
the first heating element 32, the second heating element 33 and the third heating element 34 divide the conveying pipeline 35 into a first temperature zone, a second temperature zone and a third temperature zone; for heating a solution of perovskite material fed from the seed region 2;
one end of the feed liquid circulation return area 5 is connected with the crystal collecting area 4 and is used for receiving the residual feed liquid after the perovskite single crystal material is collected in the crystal collecting area 4; the other end is connected with the seed crystal area 2 and is used for conveying the residual feed liquid to the seed crystal area.
The purification method comprises the following steps:
(1) Mixing the perovskite material prepared in examples 1 to 14 with a purification solvent to obtain a supersaturated solution of the perovskite material; and heating it; the kind of the purification solvent and the heating temperature are shown in Table 5;
(2) Conveying the supersaturated solution of the perovskite material heated in the step (1) upwards and then heating the supersaturated solution in sections; wherein the staged heating comprises a first heating stage, a second heating stage and a third heating stage; the temperatures of the first heating section, the second heating section, and the third heating section, and the conveying speed are shown in table 5.
(3) Collecting the perovskite single crystal material; and distilling the liquid by adopting a rotary evaporator, and respectively collecting the washing liquid and the by-product.
TABLE 5
Note: the upward conveying speed was calculated as 1L of the total amount of the solution in the step (1).
Effects of the embodiment
(1) Photograph
As shown in fig. 1, a photograph of the perovskite powder obtained in example 1 shows that the perovskite powder is black in color.
A photograph of the perovskite single crystal of example 15 is shown in FIG. 2, in which the grid scale is 1mm. It can be seen that the particle size of the perovskite single crystal material is in the range of 1 to 10mm, mainly distributed in the range of 3 to 6mm.
(2) Scanning electron microscope image
The scanning electron microscope image of the perovskite powder in example 1 is shown in fig. 3, and therefore, the prepared perovskite powder has a relatively regular crystal morphology, and the particle size is mainly distributed around 50 μm.
(3) X-ray diffraction pattern
The perovskite material or perovskite single crystal material prepared in the above implementation is subjected to an X-ray diffraction pattern test.
Wherein the X-ray diffraction pattern (XRD) of the perovskite powder in example 3 is shown in figure 4;
the X-ray diffraction pattern (XRD) of the perovskite powder in example 1 is shown as a in fig. 5, and the X-ray diffraction pattern (XRD) of the perovskite single crystal in example 15 is shown as b in fig. 5;
the X-ray diffraction pattern (XRD) of the perovskite powder in example 2 is shown in c of fig. 6, and the X-ray diffraction pattern (XRD) of the perovskite single crystal in example 16 is shown in d of fig. 6;
the X-ray diffraction pattern (XRD) of the perovskite single crystal of example 20 is shown in fig. 7;
the X-ray diffraction pattern (XRD) of the perovskite single crystal of example 19 is shown in fig. 8;
the X-ray diffraction pattern (XRD) of the perovskite powder in example 4 is shown as e in fig. 9, and the X-ray diffraction pattern (XRD) of the perovskite single crystal in example 18 is shown as f in fig. 9;
the X-ray diffraction pattern (XRD) of the perovskite single crystal of example 24 is shown in fig. 10;
the X-ray diffraction pattern (XRD) of the perovskite single crystal of example 21 is shown in fig. 11;
the X-ray diffraction pattern (XRD) of the perovskite single crystal in example 22 is shown in fig. 12.
As can be seen from fig. 5, 6 and 9, the FWHM of the half-value peak of the XRD diffraction peak of the purified powder is obviously smaller than that before purification, the intensity of the diffraction peak is larger, and the impurity peak before purification also disappears, which proves that the purified crystal has better quality and higher purity.
(4) 400MHz nuclear magnetic hydrogen spectrum ( 1 H NMR)
The perovskite material prepared in the above implementation is subjected to 400MHz nuclear magnetic hydrogen spectrum ( 1 H NMR).
Wherein the 400MHz nuclear magnetic hydrogen spectrum (1H NMR) of the perovskite powder in example 6 is shown in FIG. 13; as can be seen from FIG. 13, chemical shifts δ 1=2.38ppm and δ 2=7.48ppm in the nuclear magnetic hydrogen spectrum of the perovskite single crystal correspond to methylamine cation-CH, respectively 3 and-NH 3 Chemical shifts δ 3=7.85ppm, δ 4=8.66ppm and δ 5=9.01ppm respectively correspond to-CH-, -NH of the formamidine cation 2 and-NH 2+ From the integrated area, FA: MA = 1;
the 400MHz nuclear magnetic hydrogen spectrum (1H NMR) of the perovskite powder in example 4 is shown in FIG. 14-a;
the nuclear magnetic hydrogen spectrum of the perovskite powder in the embodiment 4 is shown as g in a figure 14-b, and the nuclear magnetic hydrogen spectrum of the perovskite single crystal material in the embodiment 18 is shown as h in a figure 14-b;
the 400MHz nuclear magnetic hydrogen spectrum (1H NMR) of the perovskite powder of example 8 is shown in FIG. 15;
the 400MHz nuclear magnetic hydrogen spectrum (1H NMR) of the perovskite powder in example 7 is shown in FIG. 16;
the 400MHz nuclear magnetic hydrogen spectrum (1H NMR) of the perovskite powder in example 3 is shown in FIG. 17;
the 400MHz nuclear magnetic hydrogen spectrum (1H NMR) of the perovskite powder in example 1 is shown in FIG. 18.
(5) Heat stability test
As shown in fig. 19, j is the TGA profile of the perovskite powder in example 4, and k is the TGA profile of the perovskite single crystal material in example 18. As can be seen, the temperature was 295 ℃ when the preliminary decomposition amount of the perovskite powder in example 4 reached 1%; after purification, the perovskite single crystal material of example 18 had good thermal stability as indicated by the temperature of 335 ℃ when the amount of preliminary decomposition reached 1%.
Claims (10)
1. A preparation method of a perovskite material is characterized by comprising the following steps: performing solid-phase reaction on the substance m, the substance p and the substance n;
the substance m is one or more AX; the substance p is one or more DXs; the substance n is one or more BY 2 ；
Wherein the content of the first and second substances,said A is independently Cs + Or an organic amine cation;
d is independently an organic amine cation, NH 4 + 、K + Or Na + ；
Said X is independently a halide;
said B is independently Pb 2+ 、Sn 2+ 、Ge 2+ 、Cu 2+ 、Mn 2+ 、Fe 2+ 、Bi 3+ 、Tb 3+ Or Zn 2+ ；
Y is independently CH 3 COO - 、C 2 O 4 2- 、CF 3 COO - 、CH 3 CHOHCOO - 、HCOO - 、CF 3 SO 3 - 、BF 4 - Or PF 6 - 。
2. The process for producing a perovskite material as claimed in claim 1, wherein (the amount of the substance m + the amount of the substance p): (the amount of the substance n is (1-8)): 1; preferably (2 to 5): 1; more preferably (3 to 4): 1;
and/or the molar ratio of the substance m, the substance p and the substance n is (1-4): (1-4): 1; preferably 1;
the substance m is one or two AX; preferably, when the substance m is two AX, the mass ratio of the two AX is (0.1-10): 1, preferably (0.2 to 2): 1 or (8-9): 1;
and/or the substance p is one or two DXs; preferably, when the substance p is two kinds of DX, the mass ratio of the two kinds of DX is (0.1 to 10): 1, preferably (0.2 to 2): 1 or (8-9): 1;
and/or the substance n is one or two BY 2 ；
And/or the organic amine cation is CH 3 NH 3 + 、HC(NH 2 ) 2 + 、CH 3 CH 2 NH 3 + 、CH 3 (CH 2 ) 2 NH 3 + 、CH 3 (CH 2 ) 3 NH 3 + 、CF 3 CH 2 NH 3 + 、(CH 3 ) 2 NH 2 + 、C(NH 2 ) 3 + Or
Preferably CH 3 NH 3 + 、(CH 3 ) 2 NH 2 + 、CH 3 NH 3 + Or HC (NH) 2 ) 2 + ；
And/or D is NH 4 + 、K + Or Na + ；
And/or the halide is I - 、Br - Or Cl - (ii) a Is preferably I - Or Br - ；
And/or, said B is independently Pb 2+ 、Sn 2+ 、Ge 2+ Or Cu 2+ (ii) a Preferably Pb 2+ Or Sn 2+ ；
And/or, said Y is independently HCOO - Or CH 3 COO - (ii) a Preferably CH 3 COO - 。
3. The method of preparing the perovskite material of claim 2, wherein AX is one or more of cesium iodide, methylamine hydrobromide, methylamine hydroiodide, ethylamine hydroiodide, phenethylamine hydroiodide, trifluoroethylamine hydroiodide, butylamine hydroiodide, dimethylamine hydroiodide, formamidine hydroiodide and guanidine hydroiodide; preferably methylamine hydroiodide and dimethylamine hydroiodide, or, preferably, formamidine hydroiodide and methylamine hydroiodide;
and/or DX is one or more of methylamine hydrobromide, methylamine hydroiodide, ethylamine hydroiodide, phenethylamine hydroiodide, trifluoroethylamine hydroiodide, butylamine hydroiodide, dimethylamine hydroiodide, formamidine hydroiodide, guanidine hydroiodide, sodium iodide, potassium bromide and ammonium iodide; preferably sodium iodide, potassium bromide, ammonium iodide, methylamine hydroiodide and dimethylamine hydroiodide, or formamidine hydroiodide and methylamine hydroiodide;
preferably, when the AX or the DX is methylamine hydroiodide and dimethylamine hydroiodide, the mass ratio of methylamine hydroiodide to dimethylamine hydroiodide is (8-9): 1, preferably 8.27:1;
preferably, when AX or DX is formamidine hydroiodide and methylamine hydroiodide, the mass ratio of formamidine hydroiodide to methylamine hydroiodide is (0.2 to 2): 1; preferably 1.08: 1. 0.36: 1. 0.72:1 or 1.62:1;
and/or, the BY 2 Lead acetate and/or tin acetate; BY 2 Preferably with crystal water or adsorbed water;
and/or the perovskite material has a molecular formula ABX 3 And/or A 2 BX 4 ；
The ABX 3 Preferably MAPbI 3 、MAPbBr 3 、FAPbI 3 、MA 0.9 DMA 0.1 PbI 3 、FA 0.5 MA 0.5 PbI 3 、FA 0.25 MA 0.75 PbI 3 、FA 0.4 MA 0.6 PbI 3 、FA 0.6 MA 0.4 PbI 3 、MAPb 0.5 Sn 0.5 I 3 、EAPbI 3 、GAPbI 3 Or TFEAPbI 3 ；
A is described 2 BX 4 Preferably BA 2 PbI 4 Or PEA 2 PbI 4 。
4. The method for producing a perovskite material as claimed in any one of claims 1 to 3, wherein the solid-phase reaction is grinding; the grinding temperature is preferably 20-30 ℃, and more preferably 25 ℃;
and/or after the solid phase reaction, further comprising the steps of washing and/or drying;
preferably, after the washing, the method further comprises the step of distilling or extracting the liquid collected after the washing;
more preferably, the preparation method of the perovskite material comprises the following steps: carrying out solid-phase reaction on the substance m, the substance p and the substance n to obtain a reactant; washing the reactant, and respectively collecting solid and liquid; drying the solid to obtain a perovskite material; distilling the liquid, and respectively collecting washing liquid and byproducts;
and/or the perovskite material is one or more of one-dimensional perovskite, two-dimensional perovskite and three-dimensional perovskite; preferably a two-dimensional perovskite or a three-dimensional perovskite;
the particle size of the perovskite material is preferably 3 to 6mm, for example 4 to 5mm.
5. A method of purifying a perovskite material, comprising the steps of: heating the supersaturated solution of the perovskite material in a sectional manner to obtain the perovskite single crystal material;
wherein the staged heating comprises a first heating stage, a second heating stage and a third heating stage; the temperature difference between the first heating section and the second heating section is 10-50 ℃; the temperature difference between the second heating section and the third heating section is 10-50 ℃.
6. The method of purifying a perovskite material as claimed in claim 5, wherein the perovskite material is produced by the method of producing a perovskite material as claimed in any one of claims 1 to 4;
and/or the supersaturated solution of the perovskite material is obtained by mixing the perovskite material with a purification solvent; the purifying solvent is preferably one or more of hydriodic acid aqueous solution, hydrobromic acid aqueous solution, N-dimethylformamide, dimethyl sulfoxide and gamma-butyrolactone;
and/or the temperature of the supersaturated solution of perovskite material is below the boiling point of the purification solvent; preferably 40 to 140 ℃;
and/or the supersaturated solution of the perovskite material is conveyed upwards through a conveying pipeline and then is heated in a segmented mode; wherein, when the solution volume of the perovskite material is 1L, the diameter of the conveying pipeline is preferably 1-10 cm, and more preferably 5cm; the conveying speed is preferably 5-30 mL/min; more preferably 10 to 20mL/min;
and/or the temperatures of the first heating section, the second heating section and the third heating section are preferably sequentially reduced or sequentially increased; preferably, the temperatures of the first heating section, the second heating section and the third heating section are 90 ℃, 60 ℃ and 30 ℃ respectively; or, 100 deg.C, 80 deg.C, 60 deg.C; or, 90 deg.C, 100 deg.C, 110 deg.C; or, 45 deg.C, 55 deg.C, 65 deg.C;
and/or after the supersaturated solution of the perovskite material is heated in a segmented mode, the method further comprises the step of collecting the perovskite single crystal material.
7. A perovskite single crystal material which is produced by the purification method of the perovskite material as set forth in claims 5 to 6.
8. The method of purifying a perovskite material as claimed in claim 7, wherein the perovskite single crystal material has the formula ABX 3 And/or A 2 BX 4 ；
Wherein, the ABX 3 Preferably MAPbI 3 、MAPbBr 3 、FAPbI 3 、MA 0.9 DMA 0.1 PbI 3 、FA 0.5 MA 0.5 PbI 3 、FA 0.25 MA 0.75 PbI 3 、FA 0.4 MA 0.6 PbI 3 、FA 0.6 MA 0.4 PbI 3 、MAPb 0.5 Sn 0.5 I 3 、EAPbI 3 、GAPbI 3 Or TFEAPbI 3 (ii) a A is described 2 BX 4 Preferably BA 2 PbI 4 Or PEA 2 PbI 4 ；
And/or the perovskite single crystal material is one or more of one-dimensional perovskite, two-dimensional perovskite and three-dimensional perovskite; preferably a two-dimensional perovskite or a three-dimensional perovskite;
and/or the particle size of the perovskite single crystal material is 1 to 10mm, preferably 3 to 6mm, for example 4 to 5mm.
9. Use of a perovskite single crystal material as defined in claim 7 or 8 in a solar cell.
10. A solar cell, characterized in that it comprises a perovskite single crystal material as claimed in claim 7 or 8.
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| CN110305019A (en) * | 2019-08-15 | 2019-10-08 | 暨南大学 | A kind of two-dimensional layer perovskite crystal and preparation method thereof |
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