CN113683118A - Process for preparing all-inorganic perovskite nanocrystalline by using high-energy ball milling method - Google Patents
Process for preparing all-inorganic perovskite nanocrystalline by using high-energy ball milling method Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- 238000000713 high-energy ball milling Methods 0.000 title claims abstract description 25
- 238000000498 ball milling Methods 0.000 claims abstract description 172
- 239000002159 nanocrystal Substances 0.000 claims abstract description 60
- 238000000227 grinding Methods 0.000 claims abstract description 30
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- 238000001035 drying Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 77
- 239000002244 precipitate Substances 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 22
- 238000000926 separation method Methods 0.000 claims description 22
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- 238000005119 centrifugation Methods 0.000 claims description 16
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 14
- 239000012856 weighed raw material Substances 0.000 claims description 13
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 230000008901 benefit Effects 0.000 abstract description 5
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 238000010923 batch production Methods 0.000 abstract description 2
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- 230000009467 reduction Effects 0.000 abstract description 2
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 18
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
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- 230000015572 biosynthetic process Effects 0.000 description 6
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- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- ZASWJUOMEGBQCQ-UHFFFAOYSA-L dibromolead Chemical compound Br[Pb]Br ZASWJUOMEGBQCQ-UHFFFAOYSA-L 0.000 description 3
- 238000000103 photoluminescence spectrum Methods 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 238000005349 anion exchange Methods 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
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- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- VPSXHKGJZJCWLV-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-3-(1-ethylpiperidin-4-yl)oxypyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C(=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2)OC1CCN(CC1)CC VPSXHKGJZJCWLV-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
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- 239000007850 fluorescent dye Substances 0.000 description 1
- -1 halogen ions Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
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- 238000004729 solvothermal method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/006—Compounds containing, besides lead, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
- B02C17/18—Details
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/16—Halides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
- C09K11/664—Halogenides
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
- C01P2002/34—Three-dimensional structures perovskite-type (ABO3)
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- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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Abstract
The invention relates to the technical field of nano material preparation, and discloses a process for preparing all-inorganic perovskite nano crystal by using a high-energy ball milling method, wherein the chemical formula of the all-inorganic perovskite nano crystal is CsaMbXcThe preparation process comprises the following steps: weighing, primary ball milling, secondary ball milling, cleaning, centrifuging, drying and grinding. The CsPbX with excellent light-emitting performance is prepared by adopting a high-energy ball milling method3The crystallinity, uniformity and luminescence of the finished product are good; by introducing Mn2+、Ni2+、Cu2+、Cd2+、Zn2+、Sn2+、Fe2+Plasma substitution of Pb2+To synthesize low-lead or lead-free multi-doped CsMX3The nanocrystalline realizes the effective reduction of the Pb content in the material; the method has the advantages of simple process flow, strong repeatability, small pollution in the production process, low energy consumption, wide raw material source, realization of batch production and high economic benefit.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a process for preparing all-inorganic perovskite nano crystals by using a high-energy ball milling method.
Background
In recent years, a novel all-inorganic lead-halogen perovskite nanocrystal is widely researched, and due to the excellent optical performance, the novel all-inorganic lead-halogen perovskite nanocrystal attracts great attention in the photoelectric field, such as backlight displays, solar cells, photodetectors, fluorescent probes and the like. At present, the synthesis of the all-inorganic lead halide perovskite CsPbX at home and abroad3(X＝Cl―、Br―、I―) The method of the nanocrystal is also mainly a liquid phase method, such as a high-temperature thermal injection method, a room-temperature supersaturation recrystallization method, an anion exchange method and the like. When the thermal injection method is adopted to synthesize the nanocrystalline,the reaction process needs to be carried out under the environment of high temperature and inert gas protection, and the temperature is difficult to control after the precursor solution is injected, so that the product repeatability is poor, and the problem is particularly prominent in large-scale industrial production; in addition, the size uniformity and crystallinity of the synthesized nanocrystal are poor due to the fact that the reaction process is too rapid in the room temperature supersaturation recrystallization method, in addition, the growth process of the nanocrystal and the further regulation of the luminescence performance are difficult to be kinetically controlled in the too violent and rapid reaction process, and the stability of the synthesized nanocrystal is poor; the anion exchange method can not realize the complete exchange of halogen ions, has poor repeatability, and the synthesized mixed halogen perovskite has poor stability and is especially sensitive to light. In addition, researchers have developed many other synthetic CsPbX3Liquid phase methods of nanocrystals, such as microwave, microfluidic, and solvothermal methods, but all liquid phase methods are in the synthesis of CsPbX3The process has many and complicated factors, is difficult to realize repeatable and batch preparation of high-quality nanocrystals, and inevitably uses a large amount of organic polar solvent, so the environmental problems caused by the process also attract the attention of researchers.
Therefore, a new process for preparing all-inorganic perovskite nanocrystals is needed. In addition, the toxicity of Pb in the all-inorganic lead-halogen perovskite is related to the popularization and application of the product, and is also a key problem to be solved urgently for the material.
Disclosure of Invention
The invention aims to overcome the defects and provide a process for preparing all-inorganic perovskite nanocrystals by using a high-energy ball milling method.
In order to achieve the purpose, the invention is implemented according to the following technical scheme: a process for preparing all-inorganic perovskite nanocrystalline by using a high-energy ball milling method,
the chemical formula of the all-inorganic perovskite nanocrystalline is CsaMbXcWherein X is Cl―、Br―、I―At least one of; m is Mn2+、Ni2+、Cu2+、Cd2+、Zn2+、Sn2+、Fe2+、Pb2+At least one of; c is a +2b, and a and b are positive integers;
CsaMbXcthe preparation process comprises the following steps:
1) weighing: according to CsaMbXcChemical formula (ii) weighing raw materials CsX and MX2Or/and MX2·nH2O，CsX、MX2Or/and MX2·nH2The molar ratio of O is a: b;
2) ball milling for the first time: weighing CsX and MX2Or/and MX2·nH2Putting the O into a ball milling tank, and adding grinding balls for primary ball milling;
3) ball milling for the second time: after the first ball milling is finished, adding oleylamine into the ball milling tank and then carrying out second ball milling;
4) cleaning: after the second ball milling is finished, adding methylbenzene into the ball milling tank for cleaning to obtain a mixed solution of ball-milled materials and methylbenzene;
5) centrifuging: carrying out centrifugal separation on the mixed solution to obtain a precipitate;
6) drying and grinding: drying the precipitate and grinding to obtain CsaMbXcAnd (5) obtaining a nanocrystal finished product.
Preferably, in the step 1), the weighed raw materials are dried in vacuum at 60 ℃ for 1-2 hours.
Preferably, the ball milling time of the first ball milling is 5min, and the ball milling rotating speed is 500-2500 rpm.
Preferably, the ball milling time of the second ball milling is 5-35 min, and the ball milling rotating speed is 500-2500 rpm.
Preferably, the specific process of the centrifugal separation of the mixed solution is as follows, the mixed solution is placed in a centrifuge tube for the first centrifugal separation, and then supernatant is removed; and then adding toluene into the centrifugal tube, performing secondary centrifugal separation after ultrasonic dispersion, and removing supernatant to obtain a precipitate.
Preferably, a has a value in the range of 1 or 4, and b has a value in the range of 1 or 2.
Preferably, the all-inorganic perovskite nanocrystal is CsPbX3Nanocrystal, CsPb2X5Nanocrystalline, Cs4PbX6One kind of nanocrystal.
Preferably, the chemical formula of the all-inorganic perovskite nanocrystal is CsMX3M is Mn2+、Ni2+、Cu2+、Cd2+、Zn2+、Sn2+、Fe2+、Pb2+At least two of them. When M is composed of a plurality of ions, the ratio of the total mole number of M to the mole number of Cs is 1: 1.
Preferably, CsPbX is prepared according to the steps 1) to 6)3A nanocrystal;
CsPbX obtained in step 6)3Soaking the nanocrystals in water for 2-48 h, and then transferring the nanocrystals into a centrifugal tube for centrifugal treatment; the precipitate obtained after the centrifugation is dried and grinded in vacuum to obtain CsPb2X5And (4) nanocrystals.
Preferably, the ball-to-material ratio in the ball milling process is 1-10: 1.
Preferably, in the ball milling process, the ball milling tank moves in a three-dimensional 8 shape.
Further, the invention adopts a SPEX-8000M high-energy ball mill to carry out ball milling.
The action principle of the invention is as follows:
mechanochemical synthesis of all-inorganic perovskite CsPbX3The nanocrystalline is a solid phase synthesis method, which adopts mechanical energy to activate raw materials at room temperature, changes the structure of the raw materials and induces chemical reaction, thereby forming a new phase. The method has the advantages of simple process, energy conservation, good relative repeatability, environmental friendliness and easiness in industrial production, and is a green and environment-friendly synthesis process.
The high-energy ball grinding method is different from the traditional grinding method, integrates high-energy actions such as strong impact, grinding, vibration and the like, and combines a physical method and a chemical method. Different from the two-dimensional motion mode of planetary ball milling, the high-energy ball milling performed by the high-energy ball mill is a unique three-dimensional 8-shaped motion (namely, three-dimensional infinity-shaped motion) mode, and an eccentric swing shaft is adopted; when the motor runs at a high speed, the tank body generates eccentric oscillation to drive the whole support to vibrate up and down, three-dimensional cooperative grinding including high-speed oscillation, strong impact and vibration is completed, the heat generation ratio is low, the grinding energy input is 2-3 times higher than that of the traditional planetary two-dimensional motion, the high-efficiency mechanical energy greatly improves the grinding speed and efficiency, the heat effect is reduced, the reaction activation energy can be obviously reduced, the crystal grains are refined, the sample activity is enhanced, the chemical reaction is induced, and the novel nanocrystalline is synthesized.
CsMX of the invention3(M is Mn)2+、Ni2+、Cu2+、Cd2+、Zn2+、Sn2+、Fe2+、Pb2+At least two of them), comprehensively considering tolerance factors, lattice constant difference calculation results, using Mn2+、Ni2+、Cu2+、Cd2+、Zn2+、Sn2+、Fe2+As dopant ions for partial or complete substitution of CsPbX3Pb in2+Thereby to solve CsPbX3Medium Pb toxicity, formation of low-lead or lead-free polyion-doped CsMX3And (4) nanocrystals.
For example, at Mn for two dopings2+、Ni2+、Cu2+、Cd2+、Zn2+、Sn2+、Fe2+In the method, halide raw materials of two ions are selected and mixed and ball-milled according to the respective doping molar ratio and the process of the invention, and the CsPbX is partially or completely replaced3Pb in2+Formation of low-lead or lead-free polyion-doped CsMX3A nanocrystal; at Mn in triple doping2+、Ni2+、Cu2+、Cd2+、Zn2+、Sn2+、Fe2+Selecting three kinds of ionic halide raw materials, and carrying out mixing ball milling according to the respective doping molar ratio and the process of the invention; at Mn in the case of four doping2+、Ni2+、Cu2+、Cd2+、Zn2+、Sn2+、Fe2+The four kinds of ionic halide raw materials are mixed and ball-milled according to the respective doping molar ratio and the process of the invention, and the like until the seven kinds of ions can be usedAnd doping ions.
Compared with the prior art, the invention has the following beneficial effects:
(1) the CsPbX with excellent light-emitting performance is prepared by adopting a high-energy ball milling method3Compared with the traditional liquid phase method, the process of the invention does not need high temperature, atmosphere protection and a large amount of organic solvent; compared with the traditional grinding method, the process disclosed by the invention does not need atmosphere protection and time-consuming and labor-consuming manual operation, has strong acting force on raw materials, can enable oleylamine to be in close contact with the nanocrystals, and the synthesized nanocrystal finished product has good crystallinity, uniformity and luminescence;
(2) by introducing Mn2+、Ni2+、Cu2+、Cd2+、Zn2+、Sn2+、Fe2+Plasma substitution of Pb2+To synthesize low-lead or lead-free multi-doped CsMX3The nanocrystalline realizes the effective reduction of the Pb content in the material;
(3) the method has the advantages of simple process flow, strong repeatability, small pollution in the production process, low energy consumption, wide raw material source, realization of batch production and high economic benefit.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 shows CsPbBr prepared in example 1 of the present invention3XRD pattern of the nanocrystalline finished product;
FIG. 3 shows CsPbBr prepared in examples 3 to 8 of the present invention at different amounts of oleylamine added3PL spectrum of the nanocrystal;
FIG. 4 shows CsPbBr prepared at different ball milling times in examples 9 to 14 of the present invention3PL spectrum of the nanocrystal;
FIG. 5 shows CsPbBr prepared at different ball milling times in examples 10, 12 and 14 of the present invention3A TEM image of the nanocrystal; wherein a is example 10, b is example 12, and c is example 14;
FIG. 6 shows CsPbBr prepared at different ball milling times in examples 10, 12 and 14 of the present invention3Nano meterHRTEM images of the crystals; wherein d is example 10, e is example 12, and f is example 14.
Detailed Description
The present invention will be further described with reference to specific examples, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1
As shown in figure 1, a process for preparing all-inorganic perovskite nanocrystalline with chemical formula CsPbBr by using high-energy ball milling method3；
CsPbBr3The preparation process comprises the following steps:
1) weighing: according to CsPbBr3Chemical formula (C) weighing raw materials CsBr and PbBr2，CsBr、PbBr2Weighing 5mmol of the mixture; and drying the weighed raw materials at 60 ℃ for 1-2 h in vacuum.
2) Ball milling for the first time: weighing CsBr and PbBr2Putting the mixture into a ball milling tank, and adding grinding balls (the ball-material ratio is 3.5:1) for primary ball milling; the ball milling time of the first ball milling is 5min, and the ball milling rotating speed is 1000 rpm.
3) Ball milling for the second time: after the first ball milling is finished, adding 0.4mL of oleylamine into the ball milling tank, and then carrying out second ball milling; the ball milling time of the second ball milling is 25min, and the ball milling rotating speed is 1725 rpm.
4) Cleaning: after the second ball milling is finished, adding toluene into the ball milling tank for full cleaning to obtain a mixed solution of the ball-milled materials and the toluene;
5) centrifuging: placing the mixed solution in a centrifuge tube for first centrifugal separation, and removing supernatant, wherein the centrifugation time is 10min, and the centrifugation speed is 6000 rpm; subsequently, 50mL of toluene is added into a centrifugal tube, and the ultrasonic dispersion is carried out, then the second centrifugal separation is carried out, wherein the centrifugal time is 10min, and the centrifugal speed is 10000 rpm; the supernatant was removed to obtain a precipitate.
6) Drying and grinding: the precipitate was vacuum dried at 60 ℃ for 7h and ground into a fine powder using an agate mortar to give CsPbBr3And (5) obtaining a nanocrystal finished product.
In the ball milling process of the embodiment, the ball milling tank moves in a three-dimensional 8 shape, and a SPEX-8000M high-energy ball mill is adopted for ball milling.
CsPbBr obtained in this example3The size of the nano-crystal finished product is about 9nm, the size is uniform, and the fluorescence quantum yield is 78%.
As shown in FIG. 2, CsPbBr prepared in example 1 of the present invention3XRD pattern of the nanocrystalline finished product.
Example 2
A process for preparing the full-inorganic perovskite nanocrystalline with CsPb chemical formula by high-energy ball milling2Br5；
CsPbBr was prepared according to steps 1) to 6) of example 13The nanocrystalline product is CsPbBr3Soaking the nanocrystal finished product in water for 8 hours, and transferring the nanocrystal finished product into a centrifugal tube for centrifugal treatment; centrifuging, removing supernatant, vacuum drying the obtained precipitate, and grinding to obtain CsPb2Br5And (5) obtaining a nanocrystal finished product.
CsPb obtained in this example2Br5The fluorescent quantum yield of the nanocrystal is 92%.
Example 3
A process for preparing the full-inorganic perovskite nanocrystalline with CsPbBr as chemical formula by high-energy ball milling3；
CsPbBr3The preparation process comprises the following steps:
1) weighing: according to CsPbBr3Chemical formula (C) weighing raw materials CsBr and PbBr2，CsBr、PbBr2Weighing 5mmol of the mixture; and drying the weighed raw materials at 60 ℃ for 1-2 h in vacuum.
2) Ball milling for the first time: weighing CsBr and PbBr2Putting the mixture into a ball milling tank, and adding grinding balls (the ball-material ratio is 3.5:1) for primary ball milling; the ball milling time of the first ball milling is 5min, and the ball milling rotating speed is 1000 rpm.
3) Ball milling for the second time: after the first ball milling is finished, adding 0.5mL of oleylamine into the ball milling tank, and then carrying out second ball milling; the ball milling time of the second ball milling is 20min, and the ball milling rotating speed is 1000 rpm.
4) Cleaning: after the second ball milling is finished, adding toluene into the ball milling tank for full cleaning to obtain a mixed solution of the ball-milled materials and the toluene;
5) centrifuging: placing the mixed solution in a centrifuge tube for first centrifugal separation, and removing supernatant, wherein the centrifugation time is 10min, and the centrifugation speed is 6000 rpm; subsequently, 50mL of toluene is added into a centrifugal tube, and the ultrasonic dispersion is carried out, then the second centrifugal separation is carried out, wherein the centrifugal time is 10min, and the centrifugal speed is 10000 rpm; the supernatant was removed to obtain a precipitate.
6) Drying and grinding: the precipitate was vacuum dried at 60 ℃ for 7h and ground into a fine powder using an agate mortar to give CsPbBr3And (5) obtaining a nanocrystal finished product.
In the ball milling process, the ball milling tank moves in a three-dimensional 8 shape, and a SPEX-8000M high-energy ball mill is adopted for ball milling.
Examples 4 to 8
The remaining parameters were in accordance with example 3, the amount of oleylamine added in the second ball milling in step 3) being referred to in the following table:
| oleylamine addition mL | |
| Example 4 | 0 |
| Example 5 | 0.1 |
| Example 6 | 0.2 |
| Example 7 | 0.3 |
| Example 8 | 0.4 |
As shown in FIG. 3, CsPbBr prepared in examples 3 to 8 of the present invention at different amounts of oleylamine added3PL spectrum of the nanocrystal.
Example 9
A process for preparing the full-inorganic perovskite nanocrystalline with CsPbBr as chemical formula by high-energy ball milling3；
CsPbBr3The preparation process comprises the following steps:
1) weighing: according to CsPbBr3Chemical formula (C) weighing raw materials CsBr and PbBr2，CsBr、PbBr2Weighing 5mmol of the mixture; and drying the weighed raw materials at 60 ℃ for 1-2 h in vacuum.
2) Ball milling for the first time: weighing CsBr and PbBr2Putting the mixture into a ball milling tank, and adding grinding balls (the ball-material ratio is 3.5:1) for primary ball milling; the ball milling time of the first ball milling is 5min, and the ball milling rotating speed is 1000 rpm.
3) Ball milling for the second time: after the first ball milling is finished, adding 0.4mL of oleylamine into the ball milling tank, and then carrying out second ball milling; the ball milling time of the second ball milling is 35min, and the ball milling rotating speed is 1000 rpm.
4) Cleaning: after the second ball milling is finished, adding toluene into the ball milling tank for full cleaning to obtain a mixed solution of the ball-milled materials and the toluene;
5) centrifuging: placing the mixed solution in a centrifuge tube for first centrifugal separation, and removing supernatant, wherein the centrifugation time is 10min, and the centrifugation speed is 6000 rpm; subsequently, 50mL of toluene is added into a centrifugal tube, and the ultrasonic dispersion is carried out, then the second centrifugal separation is carried out, wherein the centrifugal time is 10min, and the centrifugal speed is 10000 rpm; the supernatant was removed to obtain a precipitate.
6) Drying and grinding: the precipitate was vacuum dried at 60 ℃ for 7h and ground into a fine powder using an agate mortar to give CsPbBr3And (5) obtaining a nanocrystal finished product.
In the ball milling process of the embodiment, the ball milling tank moves in a three-dimensional 8 shape, and a SPEX-8000M high-energy ball mill is adopted for ball milling.
Examples 10 to 14
The remaining parameters correspond to those of example 9, and the milling time of the second ball milling in step 3) is as follows:
| ball milling time min | |
| Example 10 | 10 |
| Example 11 | 15 |
| Example 12 | 20 |
| Example 13 | 25 |
| Example 14 | 30 |
FIG. 5 shows C prepared at different ball milling times in examples 10, 12 and 14 of the present inventionsPbBr3A TEM image of the nanocrystal; wherein a is example 10, b is example 12, and c is example 14.
FIG. 6 shows CsPbBr prepared at different ball milling times in examples 10, 12 and 14 of the present invention3HRTEM images of nanocrystals; wherein d is example 10, e is example 12, and f is example 14.
Example 15
A process for preparing the full-inorganic perovskite nanocrystalline with CsMn chemical formula by high-energy ball milling0.2Ni0.2Cu0.2Pb0.4Cl3；
CsMn0.2Ni0.2Cu0.2Pb0.4Cl3The preparation process comprises the following steps:
1) weighing: according to CsMn0.2Ni0.2Cu0.2Pb0.4Cl3Chemical formula (b) the following raw materials 5mmol CsCl and 2mmol PbCl were weighed2、1mmol MnCl2·4H2O、1mmol NiCl2、1mmol CuCl2(ii) a And drying the weighed raw materials at 60 ℃ for 1-2 h in vacuum.
2) Ball milling for the first time: putting the weighed raw materials into a ball milling tank, and adding grinding balls (the ball-material ratio is 3.5:1) for carrying out primary ball milling; the ball milling time of the first ball milling is 5min, and the ball milling rotating speed is 1000 rpm.
3) Ball milling for the second time: after the first ball milling is finished, adding oleylamine into the ball milling tank and then carrying out second ball milling; the ball milling time of the second ball milling is 25min, and the ball milling rotating speed is 1725 rpm.
4) Cleaning: after the second ball milling is finished, adding toluene into the ball milling tank for full cleaning to obtain a mixed solution of the ball-milled materials and the toluene;
5) centrifuging: placing the mixed solution in a centrifuge tube for first centrifugal separation, and removing supernatant, wherein the centrifugation time is 10min, and the centrifugation speed is 6000 rpm; subsequently, 50mL of toluene is added into a centrifugal tube, and the ultrasonic dispersion is carried out, then the second centrifugal separation is carried out, wherein the centrifugal time is 10min, and the centrifugal speed is 10000 rpm; the supernatant was removed to obtain a precipitate.
6) Drying and grinding: the precipitate was vacuum-dried at 60 ℃ for 7 hours, and then ground into fine powder using an agate mortar to obtain CsMn0.2Ni0.2Cu0.2Pb0.4Cl3And (5) obtaining a nanocrystal finished product.
In the ball milling process of the embodiment, the ball milling tank moves in a three-dimensional 8 shape, and a SPEX-8000M high-energy ball mill is adopted for ball milling.
Example 16
A process for preparing the full-inorganic perovskite nanocrystalline with CsCd as chemical formula by high-energy ball grinding0.3Zn0.5Pb0.2Cl3；
CsCd0.3Zn0.5Pb0.2Cl3The preparation process comprises the following steps:
1) weighing: according to CsCd0.3Zn0.5Pb0.2Cl3Chemical formula (b) the following raw materials 5mmol CsCl and 1mmol PbCl were weighed2、2.5mmol ZnCl2、1.5mmol CdCl2(ii) a And drying the weighed raw materials at 60 ℃ for 1-2 h in vacuum.
2) Ball milling for the first time: putting the weighed raw materials into a ball milling tank, and adding grinding balls (the ball-material ratio is 3.5:1) for carrying out primary ball milling; the ball milling time of the first ball milling is 5min, and the ball milling rotating speed is 1000 rpm.
3) Ball milling for the second time: after the first ball milling is finished, adding oleylamine into the ball milling tank and then carrying out second ball milling; the ball milling time of the second ball milling is 25min, and the ball milling rotating speed is 1725 rpm.
4) Cleaning: after the second ball milling is finished, adding toluene into the ball milling tank for full cleaning to obtain a mixed solution of the ball-milled materials and the toluene;
5) centrifuging: placing the mixed solution in a centrifuge tube for first centrifugal separation, and removing supernatant, wherein the centrifugation time is 10min, and the centrifugation speed is 6000 rpm; subsequently, 50mL of toluene is added into a centrifugal tube, and the ultrasonic dispersion is carried out, then the second centrifugal separation is carried out, wherein the centrifugal time is 10min, and the centrifugal speed is 10000 rpm; the supernatant was removed to obtain a precipitate.
6) Drying and grinding: the precipitate was vacuum-dried at 60 ℃ for 7 hours, and then ground into fine powder using an agate mortar to obtain CsCd0.3Zn0.5Pb0.2Cl3And (5) obtaining a nanocrystal finished product.
In the ball milling process of the embodiment, the ball milling tank moves in a three-dimensional 8 shape, and a SPEX-8000M high-energy ball mill is adopted for ball milling.
Example 17
A process for preparing the full-inorganic perovskite nanocrystalline with CsMn chemical formula by high-energy ball milling0.2Ni0.2Cu0.2Sn0.2Pb0.2Cl3；
CsMn0.2Ni0.2Cu0.2Sn0.2Pb0.2Cl3The preparation process comprises the following steps:
1) weighing: according to CsMn0.2Ni0.2Cu0.2Sn0.2Pb0.2Cl3Chemical formula (b) the following raw materials 5mmol CsCl and 1mmol PbCl were weighed2、1mmol MnCl2、1mmol NiCl2、1mmol CuCl2、1mmol SnCl2(ii) a And drying the weighed raw materials at 60 ℃ for 1-2 h in vacuum.
2) Ball milling for the first time: putting the weighed raw materials into a ball milling tank, and adding grinding balls (the ball-material ratio is 3.5:1) for carrying out primary ball milling; the ball milling time of the first ball milling is 5min, and the ball milling rotating speed is 1000 rpm.
3) Ball milling for the second time: after the first ball milling is finished, adding oleylamine into the ball milling tank and then carrying out second ball milling; the ball milling time of the second ball milling is 25min, and the ball milling rotating speed is 1725 rpm.
4) Cleaning: after the second ball milling is finished, adding toluene into the ball milling tank for full cleaning to obtain a mixed solution of the ball-milled materials and the toluene;
5) centrifuging: placing the mixed solution in a centrifuge tube for first centrifugal separation, and removing supernatant, wherein the centrifugation time is 10min, and the centrifugation speed is 6000 rpm; subsequently, 50mL of toluene is added into a centrifugal tube, and the ultrasonic dispersion is carried out, then the second centrifugal separation is carried out, wherein the centrifugal time is 10min, and the centrifugal speed is 10000 rpm; the supernatant was removed to obtain a precipitate.
6) Drying and grinding: the precipitate was vacuum-dried at 60 ℃ for 7 hours, and then ground into fine powder using an agate mortar to obtain CsMn0.2Ni0.2Cu0.2Sn0.2Pb0.2Cl3And (5) obtaining a nanocrystal finished product.
In the ball milling process of the embodiment, the ball milling tank moves in a three-dimensional 8 shape, and a SPEX-8000M high-energy ball mill is adopted for ball milling.
Example 18
A process for preparing the full-inorganic perovskite nanocrystalline with CsMn chemical formula by high-energy ball milling0.1Ni0.1Cu0.2Zn0.2Sn0.2Fe0.2Cl3；
CsMn0.1Ni0.1Cu0.2Zn0.2Sn0.2Fe0.2Cl3The preparation process comprises the following steps:
1) weighing: according to CsMn0.1Ni0.1Cu0.2Zn0.2Sn0.2Fe0.2Cl3Chemical formula (A) 5mmol CsCl and 0.5mmol MnCl of the following raw materials were weighed2、0.5mmol NiCl2、1mmol CuCl2、1mmol ZnCl2、1mmol SnCl2、1mmol FeCl2(ii) a And drying the weighed raw materials at 60 ℃ for 1-2 h in vacuum.
2) Ball milling for the first time: putting the weighed raw materials into a ball milling tank, and adding grinding balls (the ball-material ratio is 3.5:1) for carrying out primary ball milling; the ball milling time of the first ball milling is 5min, and the ball milling rotating speed is 1000 rpm.
3) Ball milling for the second time: after the first ball milling is finished, adding oleylamine into the ball milling tank and then carrying out second ball milling; the ball milling time of the second ball milling is 25min, and the ball milling rotating speed is 1725 rpm.
4) Cleaning: after the second ball milling is finished, adding toluene into the ball milling tank for full cleaning to obtain a mixed solution of the ball-milled materials and the toluene;
5) centrifuging: placing the mixed solution in a centrifuge tube for first centrifugal separation, and removing supernatant, wherein the centrifugation time is 10min, and the centrifugation speed is 6000 rpm; subsequently, 50mL of toluene is added into a centrifugal tube, and the ultrasonic dispersion is carried out, then the second centrifugal separation is carried out, wherein the centrifugal time is 10min, and the centrifugal speed is 10000 rpm; the supernatant was removed to obtain a precipitate.
6) Drying and grinding: the precipitate was vacuum-dried at 60 ℃ for 7 hours, and then ground into fine powder using an agate mortar to obtain CsMn0.1Ni0.1Cu0.2Zn0.2Sn0.2Fe0.2Cl3And (5) obtaining a nanocrystal finished product.
In the ball milling process of the embodiment, the ball milling tank moves in a three-dimensional 8 shape, and a SPEX-8000M high-energy ball mill is adopted for ball milling.
Claims (9)
1. A process for preparing all-inorganic perovskite nanocrystalline by using a high-energy ball milling method is characterized by comprising the following steps:
the chemical formula of the all-inorganic perovskite nanocrystalline is CsaMbXcWherein X is Cl―、Br―、I―At least one of; m is Mn2+、Ni2+、Cu2+、Cd2+、Zn2+、Sn2+、Fe2+、Pb2+At least one of; c is a +2b, and a and b are positive integers;
CsaMbXcthe preparation process comprises the following steps:
1) weighing: according to CsaMbXcChemical formula (ii) weighing raw materials CsX and MX2Or/and MX2·nH2O，CsX、MX2Or/and MX2·nH2The molar ratio of O is a: b;
2) ball milling for the first time: weighing CsX and MX2Or/and MX2·nH2Putting the O into a ball milling tank, and adding grinding balls for primary ball milling;
3) ball milling for the second time: after the first ball milling is finished, adding oleylamine into the ball milling tank and then carrying out second ball milling;
4) cleaning: after the second ball milling is finished, adding methylbenzene into the ball milling tank for cleaning to obtain a mixed solution of ball-milled materials and methylbenzene;
5) centrifuging: carrying out centrifugal separation on the mixed solution to obtain a precipitate;
6) drying and grinding: drying the precipitate and grinding to obtain CsaMbXcAnd (5) obtaining a nanocrystal finished product.
2. The process for preparing all-inorganic perovskite nanocrystals by high energy ball milling according to claim 1, wherein:
in the step 1), the weighed raw materials are dried in vacuum at 60 ℃ for 1-2 h.
3. The process for preparing all-inorganic perovskite nanocrystals by high energy ball milling according to claim 1, wherein:
the ball milling time of the first ball milling is 5min, and the ball milling rotating speed is 500-2500 rpm.
4. The process for preparing all-inorganic perovskite nanocrystals by high energy ball milling according to claim 1, wherein:
the ball milling time of the second ball milling is 5-35 min, and the ball milling rotating speed is 500-2500 rpm.
5. The process for preparing all-inorganic perovskite nanocrystals by high energy ball milling according to claim 1, wherein: the specific process of carrying out centrifugal separation on the mixed solution is as follows, the mixed solution is placed in a centrifuge tube for carrying out first centrifugal separation, and then supernatant is removed; and then adding toluene into the centrifugal tube, performing secondary centrifugal separation after ultrasonic dispersion, and removing supernatant to obtain a precipitate.
6. The process for preparing all-inorganic perovskite nanocrystals by high energy ball milling according to claim 1, wherein: the value range of a is 1 or 4, and the value range of b is 1 or 2.
7. The process for preparing all-inorganic perovskite nanocrystals by high energy ball milling according to claim 1, wherein: the all-inorganic perovskite nanocrystal is CsPbX3Nanocrystal, CsPb2X5Nanocrystalline, Cs4PbX6One kind of nanocrystal.
8. The process for preparing all-inorganic perovskite nanocrystals by high energy ball milling according to claim 1, wherein: the chemical formula of the all-inorganic perovskite nanocrystalline is CsMX3M is Mn2+、Ni2+、Cu2+、Cd2+、Zn2+、Sn2 +、Fe2+、Pb2+At least two of them.
9. The process for preparing all-inorganic perovskite nanocrystals by high energy ball milling according to claim 7, wherein: CsPbX is prepared according to the steps 1) to 6)3A nanocrystal;
CsPbX obtained in step 6)3Soaking the nanocrystals in water for 2-48 h, and then transferring the nanocrystals into a centrifugal tube for centrifugal treatment; the precipitate obtained after the centrifugation is dried and grinded in vacuum to obtain CsPb2X5And (4) nanocrystals.
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