阅读说明：本技术 一种高稳定性金属卤化物钙钛矿纳米复合材料的制备方法 (Preparation method of high-stability metal halide perovskite nano composite material ) 是由 何培刚 赵晟坚 贾德昌 周玉 于 2020-12-08 设计创作，主要内容包括：一种高稳定性金属卤化物钙钛矿纳米复合材料的制备方法,本发明属于光电材料技术领域,它要解决金属卤化物钙钛矿CsPbX_3纳米晶稳定性不好的问题。制备方法：一、向碱激发溶液中加入活性铝硅酸盐粉体混合,倒入模具中养护,研磨后得到铝硅酸盐聚合物粉末；二、将铝硅酸盐无机聚合物粉末与水混合；三、对铝硅酸盐聚合物粉末高温处理；四、配位溶剂中加入卤化物、表面改性剂OA、OAm以及TOP混合,加热溶解；五、将铝硅酸盐聚合物粉末分散在配位溶剂中,加入卤化物前驱体,加热反应；六、经清洗和干燥。本发明采用原位合成方法,在铝硅酸盐无极聚合物的孔洞结构中原位生长出CsPbX_3纳米晶体,提高了CsPbX_3的环境稳定性。(The invention discloses a preparation method of a high-stability metal halide perovskite nano composite material, belongs to the technical field of photoelectric materials, and aims to solve the problem of CsPbX of metal halide perovskite 3 Poor stability of the nanocrystal. The preparation method comprises the following steps: firstly, adding active aluminosilicate powder into an alkali-activated solution, mixing, pouring into a mold for curing, and grinding to obtain aluminosilicate polymer powder; secondly, mixing aluminosilicate inorganic polymer powder with water; thirdly, treating the aluminosilicate polymer powder at high temperature; fourthly, adding halide, surface modifiers OA, OAm and TOP into the coordination solvent, mixing, and heating for dissolving; dispersing aluminosilicate polymer powder in a coordination solvent, adding a halide precursor, and heating for reaction; sixthly, cleaning and drying. The invention adopts an in-situ synthesis method inCsPbX in-situ grown in pore structure of aluminosilicate non-polar polymer 3 Nanocrystals, CsPbX is improved 3 Environmental stability of (c).)

1. The preparation method of the high-stability metal halide perovskite nano composite material is characterized by comprising the following steps:

firstly, mixing 20-40 g of strong base and 10-50 g of silica sol, then carrying out magnetic stirring to obtain an alkali-activated solution, then adding 12-40 g of active aluminosilicate powder, mixing, pouring into a mold after ultrasonic oscillation, carrying out curing, demolding to obtain a Cs-GP block, and grinding the block to obtain aluminosilicate inorganic polymer powder;

mixing aluminosilicate inorganic polymer powder with deionized water, carrying out ultrasonic treatment for 10-20 min, then carrying out centrifugal treatment, and sieving the powder again after centrifugation to obtain aluminosilicate polymer powder without free cesium ions;

putting the aluminosilicate polymer powder without free cesium ions into a muffle furnace, and removing adsorbed water and bound water through high-temperature treatment at 100-700 ℃ to obtain the aluminosilicate polymer powder subjected to high-temperature treatment;

fourthly, adding 0.125-1 mmol of halide, surface modifiers OA, OAm and TOP into the coordination solvent, mixing, heating at the temperature of 240 ℃ in vacuum or inert gas until the halide salt is completely dissolved, and cooling to room temperature to be used as a halide precursor;

fifthly, dispersing the aluminosilicate polymer powder after high temperature treatment in a coordination solvent, heating at the temperature of 100-290 ℃ for 20-60min, then adding the halide precursor obtained in the fourth step, and reacting at the temperature of 50-200 ℃ in an inert atmosphere to obtain CsPbBr₃-a GP composite;

sixthly, adding an organic cleaning agent into the CsPbBr obtained in the fifth step₃Drying the-GP composite material after ultrasonic centrifugation to obtain the high-stability metal halide perovskite nano composite material;

wherein the coordination solvent is one or a mixture of octadecene, trioctylphosphine oxide and thioglycollic acid; the halide in the fourth step is MnX₂、PbX₂、BiX₃X ═ Cl, Br, or I.

2. The method for preparing the high-stability metal halide perovskite nanocomposite material as claimed in claim 1, wherein the active aluminosilicate powder in the step one is metakaolin, synthetic metakaolin or Al prepared by a sol-gel method₂O₃·nSiO₂And (3) nano powder.

3. The method of preparing a high stability metal halide perovskite nanocomposite as claimed in claim 1, wherein the strong base in the first step is cesium hydroxide, potassium hydroxide or sodium hydroxide.

4. The method for preparing a high stability metal halide perovskite nanocomposite as claimed in claim 1, wherein the curing is carried out at 30 ℃ to 60 ℃ for 7 days in the first step.

5. The method for preparing a high-stability metal halide perovskite nanocomposite material as claimed in claim 1, wherein the silica alumina ratio of the aluminosilicate inorganic polymer powder obtained in the step one is 0.5-4.

6. The preparation method of the high-stability metal halide perovskite nanocomposite material as claimed in claim 1, wherein the step three is carried out at a high temperature of 250-350 ℃ for 3-5 h.

7. The method according to claim 1, wherein the halide is PbBr in step four₂Or PbBr₂And PbI₂A mixture of (a).

8. The method for preparing the high-stability metal halide perovskite nanocomposite material as claimed in claim 1, wherein the reaction is carried out at a temperature of 150-200 ℃ for 15-20 min under an inert atmosphere in the fifth step.

9. The method for preparing a high stability metal halide perovskite nanocomposite as claimed in claim 1, wherein the organic cleaning agent in the sixth step is n-hexane, isopropanol or acetone.

10. The method for preparing a high stability metal halide perovskite nanocomposite as claimed in claim 1, wherein the drying is performed at room temperature for 48h in the sixth step.

Technical Field

The invention belongs to the technical field of photoelectric materials, and particularly relates to a preparation method of a metal halide perovskite nano composite material.

Background

In recent years, metal halide perovskite is suitable for various photoelectric components due to various adjustable component structures and good photoelectric property, and shows great attraction and wide development prospect in the photoelectric field. The energy conversion efficiency of photovoltaic power generation components based on metal halide perovskites has increased to over 23% over the last decade. Due to the low preparation cost and excellent performance, the metal halide perovskite has excellent application prospect and market value in the fields of fluorescence detection, radiation detection, luminescent devices (light emitting diodes, lasers, luminescent field effect transistors) and the like.

The preparation of the metal halide perovskite at the present stage mainly adopts CsPbX₃Mainly prepared (X ═ Cl, Br and I), and can realize CsPbX with crystal size from several nanometers to several micrometers₃(X ═ Cl, Br, I). CsPbX₃Nanocrystals have received a wide attention due to their excellent optoelectronic properties, but due to CsPbX₃The poor stability of perovskite nanocrystals can degrade to various degrees in light, heat, and air, which severely limits their commercial use.

Disclosure of Invention

The invention aims to solve the problem of metal halide perovskite CsPbX₃The problem that (X ═ Cl, Br and I) nanocrystals are poor in stability is solved, and the preparation method of the high-stability metal halide perovskite nanocomposite is provided.

The preparation method of the high-stability metal halide perovskite nano composite material is realized according to the following steps:

firstly, mixing 20-40 g of strong base and 10-50 g of silica sol, then carrying out magnetic stirring to obtain an alkali-activated solution, then adding 12-40 g of active aluminosilicate powder, mixing, pouring into a mold after ultrasonic oscillation, carrying out curing, demolding to obtain a Cs-GP block, and grinding the block to obtain (micron-sized) aluminosilicate inorganic polymer powder;

mixing aluminosilicate inorganic polymer powder with deionized water, carrying out ultrasonic treatment for 10-20 min, then carrying out centrifugal treatment, and sieving the powder again after centrifugation to obtain aluminosilicate polymer powder without free cesium ions;

putting the aluminosilicate polymer powder without free cesium ions into a muffle furnace, and removing adsorbed water and bound water through high-temperature treatment at 100-700 ℃ to obtain the aluminosilicate polymer powder subjected to high-temperature treatment;

fourthly, adding 0.125-1 mmol of halide, surface modifier OA (oleic acid), OAm (oleylamine) and TOP (tri-n-octylphosphine) into the coordination solvent, mixing, heating at the temperature of 240 ℃ in vacuum or inert gas until the halide salt is completely dissolved, and cooling to room temperature to be used as a halide precursor;

fifthly, dispersing the aluminosilicate polymer powder after high temperature treatment in a coordination solvent, heating at the temperature of 100-290 ℃ for 20-60min, then adding the halide precursor obtained in the fourth step, and reacting at the temperature of 50-200 ℃ in an inert atmosphere to obtain CsPbBr₃-a GP (nano) composite;

sixthly, adding an organic cleaning agent into the CsPbBr obtained in the fifth step₃Drying the-GP composite material after ultrasonic centrifugation to obtain the high-stability metal halide perovskite nano composite material (pure CsPbBr)₃-GP nanocomposites);

wherein the coordination solvent is one or a mixture of Octadecene (ODE), trioctylphosphine oxide (TOPO) and thioglycollic acid; the halide in the fourth step is MnX₂、PbX₂、BiX₃X ═ Cl, Br, or I.

The method adopts an in-situ synthesis method to grow CsPbX in situ in a pore structure of an aluminosilicate non-polar polymer₃Nanocrystals greatly improve CsPbX₃The fluorescent material has environmental stability, so that more than 90% of fluorescent emission intensity is reserved when the fluorescent material is stored in an unprotected environment for 100 days. The invention realizes the fluorescence emission of light waves with different colors in the range of visible light (the wavelength is 380 nm-720 nm) by changing the proportion of halogen atoms.

Drawings

FIG. 1 is a metal halide perovskiteXRD diffraction pattern of (A) CsPbBr₃Standard pattern of nanocrystals, B XRD diffraction pattern of aluminosilicate inorganic polymer, C CsPbBr of example one₃-XRD diffraction pattern of GP nanocomposite;

FIG. 2 shows CsPbBr obtained in example I₃-fluorescence emission and uv absorption spectra of GP nanocomposites, wherein a denotes fluorescence emission spectra and B denotes uv absorption spectra;

FIG. 3 shows CsPbBr obtained in example I₃-scanning electron micrographs of GP nanocomposites;

FIG. 4 shows CsPbBr obtained in example I₃-GP nanocomposite transmission electron micrographs;

FIG. 5 is a fluorescence emission spectrum of the high stability metal halide perovskite-based nanocomposite obtained in example two;

FIG. 6 shows CsPbBr obtained in example one₃-GP nanocomposites stored under unprotected conditions for different times fluorescence emission spectra, wherein a represents storage for 5 days, B represents storage for 30 days and C represents storage for 90 days;

Detailed Description

The first embodiment is as follows: the preparation method of the high-stability metal halide perovskite-based nanocomposite material is realized by the following steps:

firstly, mixing 20-40 g of strong base and 10-50 g of silica sol, then carrying out magnetic stirring to obtain an alkali-activated solution, then adding 12-40 g of active aluminosilicate powder, mixing, pouring into a mold after ultrasonic oscillation, carrying out curing, demolding to obtain a Cs-GP block, and grinding the block to obtain (micron-sized) aluminosilicate inorganic polymer powder;

mixing aluminosilicate inorganic polymer powder with deionized water, carrying out ultrasonic treatment for 10-20 min, then carrying out centrifugal treatment, and sieving the powder again after centrifugation to obtain aluminosilicate polymer powder without free cesium ions;

putting the aluminosilicate polymer powder without free cesium ions into a muffle furnace, and removing adsorbed water and bound water through high-temperature treatment at 100-700 ℃ to obtain the aluminosilicate polymer powder subjected to high-temperature treatment;

fourthly, adding 0.125-1 mmol of halide, surface modifier OA (oleic acid), OAm (oleylamine) and TOP (tri-n-octylphosphine) into the coordination solvent, mixing, heating at the temperature of 240 ℃ in vacuum or inert gas until the halide salt is completely dissolved, and cooling to room temperature to be used as a halide precursor;

fifthly, dispersing the aluminosilicate polymer powder after high temperature treatment in a coordination solvent, heating at the temperature of 100-290 ℃ for 20-60min, then adding the halide precursor obtained in the fourth step, and reacting at the temperature of 50-200 ℃ in an inert atmosphere to obtain CsPbBr₃-a GP (nano) composite;

sixthly, adding an organic cleaning agent into the CsPbBr obtained in the fifth step₃Drying the-GP composite material after ultrasonic centrifugation to obtain the high-stability metal halide perovskite nano composite material (pure CsPbBr)₃-GP nanocomposites);

wherein the coordination solvent is one or a mixture of Octadecene (ODE), trioctylphosphine oxide (TOPO) and thioglycollic acid; the halide in the fourth step is MnX₂、PbX₂、BiX₃X ═ Cl, Br, or I.

The method controls the type and the proportion of the halide to obtain the B-site doped metal halide perovskite nano composite material, improves the stability of the product through doping, and regulates and controls the photoelectric properties such as emission spectrum and the like.

In the embodiment, CsPbX is grown in situ in the pore structure of aluminosilicate inorganic polymer by in-situ synthesis₃The nanocrystals utilize aluminosilicate inorganic polymers to block and isolate water and oxygen in the environment, form competition with the hydration of perovskite quantum dots, further weaken the hydration and decomposition of the perovskite quantum dots, and greatly improve CsPbX₃Environmental stability of (c).

The second embodiment is as follows: the difference between the present embodiment and the first embodiment is that the active aluminosilicate powder in the first step is metakaolin, synthetic metakaolin or Al prepared by a sol-gel method₂O₃·nSiO₂And (3) nano powder.

The third concrete implementation mode: the difference between this embodiment and the first or second embodiment is that the strong base in the first step is cesium hydroxide, potassium hydroxide or sodium hydroxide.

The fourth concrete implementation mode: this embodiment is different from one of the first to third embodiments in that the curing is performed at 30 to 60 ℃ for 7 days in the first step.

The fifth concrete implementation mode: this embodiment is different from one of the first to fourth embodiments in that the aluminosilicate inorganic polymer powder obtained in the first step has a silica alumina ratio of 0.5 to 4.

The sixth specific implementation mode: the difference between this embodiment and the first to the fifth embodiment is that the third step is performed at a high temperature of 250-350 ℃ for 3-5 hours.

The seventh embodiment: this embodiment is different from the first to the sixth embodiment in that the halide in the fourth step is PbBr₂Or PbBr₂And PbI₂A mixture of (a).

The embodiment controls the proportion of the halogen element in the precursor, and further controls the proportion of the halogen atom in the product, so that the fluorescence emission of different colors of light in the range of visible light (the wavelength is 380 nm-720 nm) can be realized.

The specific implementation mode is eight: the difference between the present embodiment and one of the first to seventh embodiments is that in the fifth step, the reaction is performed at a temperature of 150 to 200 ℃ for 15 to 20min under an inert atmosphere.

The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is that the organic cleaning agent in the sixth step is n-hexane, isopropanol or acetone.

The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is that in the sixth step, the drying is performed at room temperature for 48 hours.

Example (b): the preparation method of the high-stability metal halide perovskite-based nanocomposite material is realized by the following steps:

firstly, mixing 33g of cesium hydroxide and 30g of silica sol, magnetically stirring for 96 hours to obtain an alkali-activated solution, then adding 4g of metakaolin powder, mixing, ultrasonically vibrating for 30min, pouring into a mold, curing for 7 days at 80 ℃, demolding to obtain a Cs-GP block, grinding the block, and sieving with a 200-mesh sieve to obtain (micron-sized) aluminosilicate inorganic polymer powder (the silica-alumina ratio is 2.25);

mixing aluminosilicate inorganic polymer powder with deionized water, performing ultrasonic treatment for 10min, performing centrifugal treatment at 3000r/min, and sieving the centrifuged powder with a 200-mesh sieve again to obtain aluminosilicate polymer powder without free cesium ions;

putting the aluminosilicate polymer powder without free cesium ions into a muffle furnace, and performing high-temperature treatment at 300 ℃ for 5 hours to remove adsorbed water and bound water to obtain the aluminosilicate polymer powder subjected to high-temperature treatment;

fourthly, taking 25mL of Octadecene (ODE) as a coordination solvent, and adding 0.395mmol of PbBr into the coordination solvent₂Mixing 5ml of surface modifier OA (oleic acid), 5ml of OAm (oleylamine) and 3ml of TOP (tri-n-octylphosphine), heating at 240 ℃ in vacuum or inert gas until lead halide salt is completely dissolved, and cooling to room temperature to be used as a lead halide precursor;

fifthly, dispersing 5g of high-temperature treated aluminosilicate polymer powder in 25mL of coordination solvent, heating at 240 ℃ for 60min, adding the lead halide precursor obtained in the fourth step, and reacting at 200 ℃ for 15min in an inert atmosphere to obtain CsPbBr₃-a GP (nano) composite;

sixthly, adding normal hexane into the CsPbBr obtained in the fifth step₃Ultrasonically centrifuging the-GP composite material, and drying the-GP composite material for 48 hours at room temperature to obtain the high-stability metal halide perovskite nano composite material (pure CsPbBr)₃-GP nanocomposites.

CsPbBr obtained in this example₃The fluorescence emission spectrum peak position of the nano composite material is about 525nm, which is consistent with the theoretical calculation value, and the fluorescence emission intensity of the powder after being processed at 80 ℃ is kept above 90 percent of that of the unprocessed powder. The fluorescence emission intensity of the powder is kept above 92% of that of the untreated powder after the powder is placed in the environment without the protection of protective atmosphere for 180 days.

Example two: this exampleDifferent from the first embodiment, 0.120mmol of PbBr was used in the fourth step₂And 0.276mmol of PbI₂And (3) mixing. Other steps and parameters are the same as in the first embodiment.

The peak position of the emission spectrum of the metal halide perovskite nano composite material obtained by the embodiment is about 620 nm.