CN115873597A - Method for batch preparation of lead-free perovskite luminescent material at room temperature - Google Patents
Method for batch preparation of lead-free perovskite luminescent material at room temperature Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
The invention relates to a method for preparing a lead-free perovskite luminescent material in batches at room temperature. The method takes chloride, carbonate, acetate or oxide as raw materials, and obtains the lead-free double perovskite luminescent material by adding a small amount of hydrochloric acid, then carrying out ultrasonic treatment and stirring. The invention does not need steps of grinding, dissolving and the like, has short required time, high yield, low cost, large batch, no high temperature and no high pressure, and the obtained micron-sized particle powder has excellent qualities of high luminous efficiency, uniform appearance/luminescence, good light/heat stability, easy doping, realization of various luminescence regulation and control and the like.
Description
The technical field is as follows:
the invention relates to the field of luminescent material preparation, in particular to a method for preparing a lead-free perovskite luminescent material at room temperature in batches.
Background art:
the lead-free perovskite material overcomes the defect of the traditional lead-based perovskite material (APbX) 3 A is a monovalent organic or inorganic ion or cluster; x is halogen Cl/Br/I) is considered one of the competitive luminescent candidates. Thanks to the soft lattice, the material forms a self-trapping state upon excitation due to local lattice distortion, thereby exhibiting a broadband emission characteristic (e.g. Cs) 2 Na 1-x Ag x In 1-y Bi y Cl 6 The luminous wave band is about 400-900 nm), is friendly to human eyes, and can well meet the requirements of white light LEDs or LCD liquid crystal screen backlight sources and the like. On the premise of ensuring bright luminescence of the product, a ringAn environmentally friendly rapid batch preparation is highly appreciated and one of the prerequisites for industrial application.
Both the traditional high-temperature solid phase method and the hydrothermal method need a high-temperature environment, and the preparation period is long, generally tens of hours. In addition, both of these solutions show certain risk factors, such as the release of harmful gases from the high temperature solid phase (e.g. chlorides can generate chlorine at high temperatures) and the high pressure environment requirements of hydrothermal processes. In contrast, chemical synthesis schemes typified by recrystallization require milder, cs 2 (Ag/Na)InCl 6 For example, csCl, agCl and NaCl as raw materials are dissolved in a selected solvent to form a precursor solution, and the precursor solutions are mixed with each other or added to an anti-solvent, so that the product is precipitated in the form of a precipitate. Among chemical solvents, concentrated hydrochloric acid is considered to be an excellent solvent due to its chlorine-rich environment to reduce the number of surface defects. However, preparation of e.g. Cs 2 (Ag/Na)InCl 6 Or Cs 2 ZrCl 6 Unavoidable raw materials such as AgCl, naCl and ZrCl used for the materials 4 The solubility in concentrated hydrochloric acid is extremely low, resulting in a large consumption of concentrated hydrochloric acid, for example up to 30mL of concentrated hydrochloric acid for 1mmol of product. In order to increase the solubility of the starting material, numerous scholars choose to increase the temperature appropriately (for example 80-115 ℃), but this temperature exceeds the boiling point of concentrated hydrochloric acid (about 45-48 ℃), resulting in a considerable evaporation of the HCl gas and thus in a reduction of the hydrochloric acid concentration, while a lower hydrochloric acid concentration causes a lower yield, impaired luminescence and a mixed crystalline phase. To date, the scientific research and industrial industries still lack a preparation scheme which can simultaneously meet the requirements of no high temperature, no high pressure, environmental friendliness, short time, low cost and high yield. This is also one of the core factors that currently limit the lead-free perovskite materials to the commercial market, and it is a problem in the scientific and industrial fields to develop a preparation strategy that can simultaneously meet the above requirements.
In the prior art, the literature of Dalton trans, 2020,49,15231 reports the synthesis of Cs by room temperature method 2 Na 1- x Ag x InCl 6 A double perovskite material. The authors add 1mmol NaCl,1-x mmol AgCl and x mmol InCl to the starting material 3 Dissolving the mixture into 30mL of concentrated hydrochloric acid,then 2mL of concentrated hydrochloric acid precursor (1 mmol/mL) in which CsCl is dissolved is added into the solution, and the product can be obtained.
The literature inorg. Chem. Front.,2021,8,4035 reports room temperature synthesis of Cs 2 ZrCl 6 A double perovskite material. The authors dissolved 2mmol CsCl in 10mL concentrated HCl, 1mmol ZrCl 4 Dissolving the CsCl precursor in 8mL of concentrated hydrochloric acid, and dropwise adding the CsCl precursor into ZrCl 4 Stirring the precursor continuously to obtain the final Cs 2 ZrCl 6 And (3) fluorescent powder.
The document adv. Opt. Mater, 2022,10,2101661 reports the wet milling process for the preparation of Rb 2 ZrCl 6 RbCl and ZrCl are weighed in proportion 4 Adding a proper amount of acetone into a mortar, grinding for 20 minutes, and obtaining a final product after the acetone is volatilized.
However, these methods have problems of complicated production equipment, long cycle, low yield, large solvent consumption, high production temperature, and the like, and the main cause of these methods is poor solubility of the raw material, for example, the solubility of AgCl in concentrated hydrochloric acid is less than 0.0019mg/mL (this is the solubility of silver chloride in pure water).
The invention content is as follows:
the invention aims to provide a method for preparing a lead-free perovskite luminescent material at room temperature in batches aiming at the existing preparation problems. The method takes chloride, carbonate, acetate or oxide as raw materials, and obtains the lead-free double perovskite luminescent material by adding a small amount of hydrochloric acid, then carrying out ultrasonic treatment and stirring. The invention does not need steps of grinding, dissolving and the like, has short required time, high yield, low cost, large batch, no high temperature and no high pressure, and the obtained micron-sized particle powder has excellent qualities of high luminous efficiency, uniform appearance/luminescence, good light/heat stability, easy doping, realization of various luminescence regulation and control and the like.
The technical scheme of the invention is as follows:
a method for preparing a lead-free perovskite luminescent material in batches at room temperature comprises the following steps:
(1) Selecting related compounds according to the element composition of the perovskite chemical formula, and preparing materials according to the element proportion;
wherein the perovskite is preferably Cs 2 ZrCl 6 Or Cs 2 Na 1-x Ag x In 1-y Bi y Cl 6 X is more than or equal to 0 and less than or equal to 1, and y is more than or equal to 0 and less than or equal to 1; the subscript number is the atomic number ratio of each element in the molecular formula;
Cs 2 ZrCl 6 the compounds related to the perovskite are Cs-containing compounds and Zr-containing compounds;
Cs 2 Na 1-x Ag x In 1-y Bi y Cl 6 the perovskite related compounds are Na-containing compounds, in-containing compounds, bi-containing compounds, cs-containing compounds and Ag-containing compounds;
the various compounds described are all non-oxides.
The Cs-containing compound is CsCl or Cs 2 CO 3 ；
The Zr-containing compound is ZrCl 4 Or Zr (CO) 3 ) 2 ；
The Ag-containing compound is AgCl or CH 3 COOAg；
The Na-containing compound is NaCl or NaHCO 3 Or Na 2 CO 3 ；
The In-containing compound is InCl 3 Or In (CH) 3 COO) 3 ；
The Bi-containing compound is BiCl 3 Or Bi (CH) 3 COO) 3 ；
(2) Adding hydrochloric acid into the above mixture, performing ultrasonic treatment for 1-5min, and stirring at 1000-8000rpm for 1-5min;
wherein, 0.5-10mL hydrochloric acid is added into each 1mmol target perovskite; the concentration of hydrochloric acid is 15-35wt%;
after adding hydrochloric acid, shaking the mixture before ultrasonic treatment;
(3) And centrifuging the product obtained in the last step, removing supernatant, washing the precipitate with ethanol, and drying to obtain the corresponding perovskite.
The invention has the substantive characteristics that:
currently prepared Cs 2 Na 1-x Ag x In 1-y Bi y Cl 6 (0. Ltoreq. X.ltoreq.1 ) is usually a recrystallization method which requires the starting materials to be dissolved in a corresponding solvent and then added dropwise to an antisolvent to give the product. By utilizing the method, when the chloride lead-free perovskite material is prepared, the raw materials are respectively and completely dissolved in concentrated hydrochloric acid and then mixed to obtain a product, so that the consumption of the hydrochloric acid is extremely high, the yield is extremely low, and if 1mmol of the product needs to consume 30mL of concentrated hydrochloric acid;
in the present invention, the raw materials are not required to be dissolved, and particularly, the raw materials are not required to be dissolved separately as in the conventional method, but all the powder raw materials are mixed together, and then a small amount of concentrated hydrochloric acid (0.5 to 10mL of concentrated hydrochloric acid corresponding to 1mmol of the product) is added dropwise, and then the mixture is subjected to ultrasonic treatment and stirring to obtain the product, and steps such as grinding and the like which cannot be mass-produced are not required.
The continuous process of gradually dissolving the raw material into free ions, recombining the free ions and recombining the free ions to separate out the product is macroscopically represented as a rapid conversion process from a solid raw material to a solid product; microscopically, the ion reaction formula in the dissolving process is shown as the formula (1-3) (chloride raw material and synthetic Cs 2 AgInCl 6 For example):
CsCl＝Cs + +Cl - (1)
InCl 3 ＝In 3+ +3Cl - (2)
for the region where each source ion is sufficient, according to the theory of lowest energy, each ion can be rapidly combined to form a product and be precipitated in the form of precipitate, as shown in formula (4):
notably, the solubility of AgCl in concentrated HCl relative to CsCl and InCl 3 Low and thus, exhibits an Ag-poor environment in the solvent, resulting in the formation of an intermediate product Cs 2 InCl 5 ·H 2 O is represented by the formula (5). But AgCl still can slowly release Ag + And the intermediate product is combined with the intermediate product to generate a final target product through a secondary reaction, wherein the final target product is shown as a formula (6).
Ag in the formula (6) + And (3) continuously consuming, so that the chemical equilibrium In the formula (3) is continuously pushed to the right until the AgCl raw material is completely consumed, and if the charge ratio of Cs, ag and In is 2 2 InCl 5 ·H 2 O will also be consumed exactly synchronously to complete, producing pure phase Cs 2 AgInCl 6 And (4) obtaining a product.
In addition, if the starting material is a non-chloride, concentrated hydrochloric acid will react to form chloride as cesium carbonate Cs 2 CO 3 And silver acetate CH 3 COOAg, for example, as shown in formula (7-8), the above process can still be continued.
The invention has the following beneficial effects:
1. by utilizing the preparation scheme of the invention, the preparation period of various chloride materials is accelerated from hour level to several minutes or even tens of seconds, and the time cost is reduced by magnitude order.
2. By using the preparation scheme of the invention, taking 1mmol of product as an example, the usage amount of concentrated hydrochloric acid is reduced from tens of milliliters to 2mL at the lowest, and the usage amount of solvent is reduced by orders of magnitude.
3. Product Cs obtained by the preparation scheme of the invention 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The luminescence quantum efficiency reaches (98.3 + -3.8)%, which may be the current Cs according to research 2 Na 1-x Ag x In 1-y Bi y Cl 6 (0. Ltoreq. X.ltoreq.1, 0. Ltoreq. Y.ltoreq.1) the highest luminescent quantum efficiency among the series of materials can be found in Nature,2018,563,541-545. The quantum efficiency reported in this document is (86. + -.5)%
4. By utilizing the preparation scheme of the invention, the preparation can be carried out at room temperature only by one test tube, the preparation process does not depend on equipment such as high temperature, high pressure and the like, and the preparation device is simplified (for example, a condensation device for preventing hydrochloric acid from volatilizing or a series of devices which are not suitable for industrial production such as a liquid nitrogen cold trap and the like are omitted).
Compared with the existing chloride preparation scheme mainly based on perovskite materials, the preparation scheme provided by the invention can simultaneously meet the industrial requirements of no high temperature, no high pressure, environmental friendliness, short time, low cost, high yield, large batch and the like, and the synthesized sample has excellent light and heat stability.
Description of the drawings:
FIG. 1 shows Cs obtained in example 1 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 XRD pattern of (a);
FIG. 2 shows Cs obtained in example 1 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 A luminescence spectrum of (a);
FIG. 3 shows Cs obtained in example 1 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The chemical yield and the luminous intensity of the compound are plotted against the concentration of hydrochloric acid;
FIG. 4 shows Cs obtained in example 1 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 XRD of (1) is plotted along with the concentration of hydrochloric acid;
FIG. 5 shows Cs obtained in example 1 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The chemical yield and the luminous intensity of the compound are plotted against the dosage of concentrated hydrochloric acid;
FIG. 6 shows Cs obtained in example 1 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The temperature-variable spectrogram of (1);
FIG. 7 shows Cs obtained in example 1 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The luminous intensity of the light source is plotted against the temperature change;
FIG. 8 shows Cs obtained in example 1 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 Thermal fatigue test chart of (1);
FIG. 9 shows Cs obtained in example 1 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 Thermal stability test chart of (1);
FIG. 10 shows Cs obtained in example 1 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The photostability test chart of (1);
FIG. 11 shows Cs obtained in example 2 2 Na 1-x Ag x InCl 6 XRD patterns of the series of samples;
FIG. 12 shows Cs obtained in example 2 2 Na 1-x Ag x InCl 6 Emission spectra of the series of samples;
FIG. 13 shows Cs obtained in example 2 2 Na 1-x Ag x InCl 6 Chemical yield and luminescence intensity of the series of samples are related to the value of x;
FIG. 14 shows Cs obtained in example 3 2 Na 0.9 Ag 0.1 In 1-y Bi y Cl 6 XRD patterns of the series of samples;
FIG. 15 shows Cs obtained in example 3 2 Na 0.9 Ag 0.1 In 1-y Bi y Cl 6 Emission spectra of the series of samples;
FIG. 16 shows Cs obtained in example 3 2 Na 0.9 Ag 0.1 In 1-y Bi y Cl 6 Chemical yield and luminescence intensity of the series of samples are related to the y value;
FIG. 17 shows Cs obtained in example 4 2 ZrCl 6 XRD pattern of the sample;
FIG. 18 shows Cs obtained in example 4 2 ZrCl 6 An emission spectrum of the sample;
FIG. 19 shows Cs obtained in example 4 2 ZrCl 6 An excitation spectrum of the sample;
FIG. 20 shows Cs obtained in example 4 2 ZrCl 6 The chemical yield and the luminous intensity of the sample are plotted against the concentration of hydrochloric acid;
FIG. 21 shows Cs obtained in example 4 2 ZrCl 6 The chemical yield and the luminous intensity of the sample are plotted against the dosage of concentrated hydrochloric acid;
FIG. 22 shows Cs obtained in example 4 2 ZrCl 6 A thermal stability test profile of the sample;
FIG. 23 shows Cs obtained in example 5 2 Na 0.9 Ag 0.1 InCl 6 10% XRD pattern of Cr sample;
FIG. 24 shows Cs obtained in example 5 2 Na 0.9 Ag 0.1 InCl 6 10% the luminescence spectrum of the Cr sample;
FIG. 25 shows Cs obtained in example 6 2 Na 0.9 Ag 0.1 InCl 6 10% XRD pattern of Tb sample;
FIG. 26 shows Cs obtained in example 6 2 Na 0.9 Ag 0.1 InCl 6 10% the luminescence spectrum of Tb sample;
FIG. 27 shows Cs obtained in example 7 2 Na 0.9 Ag 0.1 InCl 6 10% XRD pattern of Tm sample;
FIG. 28 shows Cs obtained in example 7 2 Na 0.9 Ag 0.1 InCl 6 10% the emission spectrum of the Tm sample;
FIG. 29 shows Cs obtained in example 8 2 ZrCl 6 5% XRD pattern of the Sb sample;
FIG. 30 shows Cs obtained in example 8 2 ZrCl 6 5% emission spectrum of the Sb sample;
FIG. 31 shows Cs obtained in example 9 2 ZrCl 6 5% XRD pattern of Bi sample;
FIG. 32 shows Cs obtained in example 9 2 ZrCl 6 5% emission spectrum of the Bi sample;
FIG. 33 shows Cs obtained in example 10 2 ZnCl 4 5% XRD pattern of Ce samples;
FIG. 34 shows Cs obtained in example 10 2 ZnCl 4 5% emission spectrum of the Ce sample;
the specific implementation mode is as follows:
example 1: representative samples obtained using the preparation protocol of the present invention are shown.
The preparation method comprises the following steps: to prepare 1mmol of Cs 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 For example, 2mmol CsCl (0.3367 g), 0.9mmol NaCl (0.0526 g), 0.1mmol AgCl (0.0143 g), 0.95mmol InCl were weighed out 3 ·4H 2 O (0.2785 g) and 0.05mmol of BiCl 3 (0.0158 g) A small amount of 35wt% concentrated hydrochloric acid (2 mL for this particular experiment) was added to the tube, and after shaking the mixture for about 1 minute with appropriate stirring, the mixture was shaken at 0.5W/cm 2 Sonication for about 5 minutes followed by stirring at 6000rpm for about 5 minutes gave a bright luminescent product.
After the preparation is finished, the mixture is centrifuged for 2-3 times at 5000rpm-10s, and then is washed by ethanol, and the final precipitate is put into an oven and dried for about 2 hours at 60 ℃ to obtain a sample in the form of final powder.
And (3) testing conditions are as follows: a Rigaku X-ray diffractometer is adopted to test the crystal structure of a sample, a radiation source is a Cu target, the tube voltage is 40kV, the tube current is 40mA, the scanning step is 0.02 degrees, the scanning speed is 15 degrees/min, and the scanning range is 10 degrees to 70 degrees. The emission spectrum, excitation spectrum, quantum yield (PLQY) and temperature-variable spectrum (realized by connecting with a temperature-controlled sample tank) of the sample are obtained by testing through an FLS1000 spectrometer.
The experimental results are as follows: FIG. 1 shows a sample Cs 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 From the results of XRD tests, it can be seen that according to the preparation scheme of the present invention, the diffraction peak of the product corresponds to the peak position of the standard card, indicating that the crystalline phase of the target product has been obtained.
FIG. 2 shows the sample Cs 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The spectrum test result is consistent with the luminescence wave band and the spectrum shape reported in scientific research articles.
FIG. 3 shows the sample Cs 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The relationship graph of the chemical yield and the luminescence intensity with the hydrochloric acid concentration shows that the yield of the sample is kept in the range of 90-95% in the concentration range of 25-35wt%, and the chemical yield and the luminescence intensity of the product are obviously reduced along with the reduction of the hydrochloric acid concentration to the vicinity of 15 wt%. This result indicates that the concentrated hydrochloric acid environment of the present invention is one of the most important factors for successful sample synthesis. In conjunction with the subsequent fig. 4, it can be seen that after the hydrochloric acid concentration is reduced, impurities appear in the phase of the product, resulting in a reduction in the luminous intensity; the decrease in chemical yield is due to the inability of the solvent to provide Cl-rich solution due to the decrease in hydrochloric acid concentration - The environment increases the solubility of the product, which makes the product difficult to separate out.
FIG. 4 shows the sample Cs 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The XRD results of (1) were varied with the hydrochloric acid concentration, and it was observed that when the hydrochloric acid concentration was decreased to 15wt%, the phase of the product was changed, and more heterogeneous products were produced, possibly classified as Cs 2 InCl 5 ·H 2 O and CsAgCl 2 And the like. This result corresponds to a sudden change in the luminous intensity and yield at 15wt% in fig. 3, and a change in the phase is one of the factors.
FIG. 5 is a graph showing the relationship between the yield and the luminescence intensity of the sample and the amount of concentrated hydrochloric acid, and it can be seen that when the target 1mmol product is proportioned, the yield is 90% -95% and the luminescence intensity is basically stable when the amount of concentrated hydrochloric acid is less than 5mL, which is consistent with the conclusion in FIG. 3; after the dosage of the hydrochloric acid is further increased, the yield and the luminous intensity are slightly reduced, but still more than 80 percent is kept, which shows that the dosage range of the concentrated hydrochloric acid is wider.
FIG. 6 shows the sample Cs 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The variable-temperature emission spectrum in the temperature range of 123-473K can see that the luminescence peak shape and the peak position of the sample are kept fixed, which indicates that the sample has pure crystal phase and a unique self-trapping luminescence center.
FIG. 7 shows the sample Cs 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The integrated intensity change of the temperature-shifted emission spectrum in the temperature range of 123-473K, it can be seen that the luminescence intensity decreases to 94.21% and 72.22% of the initial intensity when increasing to about 0 ℃ (273K) and 150 ℃ (423K), respectively, exhibiting good thermal stability, indirectly indicating the reliability of the preparation scheme of the present invention.
FIG. 8 shows the sample Cs 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The change of the luminous intensity in the cyclic temperature rise-temperature fall at 25-200 ℃ shows that after the cyclic time reaches 3 times, the sample is continuously stabilized to be near 93% of the initial luminous intensity, the sample shows excellent fatigue resistance to the temperature, and the reliability of the preparation scheme of the invention is indirectly shown.
FIG. 9 shows the sample Cs 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The change in luminescence intensity during the 1000h heating duration, after the 1000h heating duration, the sample stabilized around 90% of the initial intensity, consistent with the fatigue resistance test results of fig. eight, exhibiting excellent thermal stability, indirectly indicating the reliability of the inventive preparation protocol.
FIG. 10 shows the sample Cs 2 Na 0.9 Ag 0.1 In 0.95 Bi 0.05 Cl 6 The change of the luminous intensity in the continuous ultraviolet irradiation process is that after 1000h of continuous irradiation, the sample is stabilized to be about 95 percent of the initial intensity, and the sample shows excellent light irradiation stabilityThe reliability of the preparation scheme of the invention is shown.
Example 2: the scheme of the invention is utilized to realize the development of perovskite material series 1
The preparation method comprises the following steps: to prepare 1mmol of Cs 2 Na 1-x Ag x InCl 6 For an example (where x =0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9, 1.0), 2mmol CsCl (0.3367 g), 1-x mmol NaCl, x mmol AgCl and 1mmol InCl were weighed out 3 ·4H 2 O (0.2932 g), each of the raw material combinations was placed in 11 test tubes according to the value of x, a small amount of 35wt% concentrated hydrochloric acid (2 mL was used in the experiment) was added, and the mixture was stirred appropriately for about 1 minute and then at 0.5W/cm 2 And (4) carrying out ultrasonic treatment for about 5 minutes, and then stirring at 6000rpm for about 5 minutes to obtain a corresponding luminescent product.
After the preparation is finished, centrifuging the mixture of each test tube at 5000rpm-10s, washing with ethanol for 2-3 times, respectively placing the final precipitates into an oven, and drying at 60 ℃ for about 2 hours to obtain a sample in the form of final powder.
And (3) testing conditions: same as in example 1.
The experimental results are as follows: FIG. 11 shows a series of samples Cs 2 Na 1-x Ag x InCl 6 From the results of XRD tests, it can be seen that according to the preparation scheme of the present invention, the diffraction peak of the product corresponds to the peak position of the standard card, indicating that the crystalline phase of the target product has been obtained. Diffraction peaks near about 14.5 ° and 29.5 ° gradually decreased with increasing Ag content, demonstrating successful alloying of Na — Ag.
FIG. 12 shows a series of samples Cs 2 Na 1-x Ag x InCl 6 The emission spectrum test result of (1) shows that the luminescence of the sample gradually decreases after the sample shows a sudden increase along with the alloying of Na-Ag, and as shown by a circular dotted line in a subsequent figure 13 (the circular dotted line reaches the maximum when x = 0.1), the scheme of the invention also shows that the performance regulation of the luminescence of the sample can be realized.
FIG. 13 shows a series of samples Cs 2 Na 1-x Ag x InCl 6 The yield and the luminous intensity of the sample are changed along with the change of the ratio of Ag to Na, and the yield of the sample is still maintainedAround 90%, similar to case 1; at Ag content x =0.1, the corresponding sample exhibited the most prominent luminescence intensity. And the luminous intensity gradually decreases along with the increase of the Ag content, and the luminous intensity is highest when the Ag content x = 0.1.
Example 3: the scheme of the invention is utilized to realize the development of perovskite material series 2
The preparation method comprises the following steps: to prepare 1mmol of Cs 2 Na 0.9 Ag 0.1 In 1-y Bi y Cl 6 For an example (where y =0,0.01,0.05,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9, 1.0), 2mmol CsCl (0.3367 g), 0.9mmol NaCl (0.0526 g), 0.1mmol AgCl (0.0143 g), 1-y mmol InCl were weighed 3 ·4H 2 O and y mmol of BiCl 3 According to the value of y, the raw material combinations were placed in 13 test tubes, a small amount of 35wt% concentrated hydrochloric acid (2 mL was used in the experiment) was added, and the mixture was stirred appropriately for about 1 minute and then at 0.5W/cm 2 Sonication for about 5 minutes followed by stirring at 6000rpm for about 5 minutes gave a bright luminescent product.
After the preparation is finished, centrifuging the mixture of each test tube at 5000rpm-10s, washing with ethanol for 2-3 times, putting the final precipitate into respective ovens, and drying at 60 ℃ for about 2 hours to obtain a sample in the form of final powder.
And (3) testing conditions are as follows: same as in example 1.
The experimental results are as follows: FIG. 14 shows a series of samples Cs 2 Na 0.9 Ag 0.1 In 1-y Bi y Cl 6 From the results of XRD tests, it can be seen that according to the preparation scheme of the present invention, the diffraction peak of the product corresponds to the peak position of the standard card, indicating that the crystalline phase of the target product has been obtained. The gradual forward shift of the main peak position from 23.9 ° to 23.2 ° can be seen In the right panel, indicating successful alloying of In — Bi.
FIG. 15 shows a series of samples Cs 2 Na 0.9 Ag 0.1 In 1-y Bi y Cl 6 The emission spectrum test result of (1) shows that the luminescence waveband of the sample gradually red-shifts from 600nm to 700nm with the increase of Bi content, which is attributed to direct band gapThe change of the indirect band gap also shows that the scheme of the invention can realize the performance regulation of the sample luminescence and also shows the successful alloying of In-Bi.
FIG. 16 shows a series of samples Cs 2 Na 0.9 Ag 0.1 In 1-y Bi y Cl 6 The yield and the luminous intensity of the light-emitting diode are changed along with the In-Bi ratio, and the light-emitting diode has a Bi content of y<At 0.2, the yield of the sample remained around 90%, as in protocol 1, at y>When 0.2 hour, the yield is slightly reduced, but can still be maintained above 80 percent; at a Bi content x =0.05, the corresponding sample exhibited the most prominent luminescence intensity. When the Ag content is fixed to x =0.1, and the Bi content y =0.05, the luminous intensity of the sample is optimal.
Example 4: the scheme in the invention is utilized to realize the expansion of other derivative perovskite material series 3
The preparation method comprises the following steps: to prepare 1mmol of Cs 2 ZrCl 6 For example, 2mmol CsCl (0.3367 g), 1mmol ZrCl were weighed 4 (0.2330 g) A small amount of 35wt% concentrated hydrochloric acid (2 mL for this particular experiment) was added to the tube and the mixture was stirred at 1000rpm for about 1 minute to give a bright, luminescent product.
After the preparation is finished, the mixture is centrifuged for 2-3 times at 5000rpm-10s, and then is washed by ethanol, and the final precipitate is put into an oven and dried for about 2 hours at 60 ℃ to obtain a sample in the form of final powder.
And (3) testing conditions are as follows: same as in example 1.
The experimental results are as follows: FIG. 17 shows the sample Cs 2 ZrCl 6 As a result of XRD test, it can be seen that according to the preparation scheme of the present invention, the diffraction peak of the product corresponds to the peak position of the standard card, indicating that the crystalline phase of the target product has been obtained.
FIG. 18 shows sample Cs 2 ZrCl 6 As can be seen from the results of the emission spectrum test, the emission spectrum of the obtained product according to the preparation scheme of the present invention is the same as that reported in the previous literature.
FIG. 19 shows the sample Cs 2 ZrCl 6 The excitation spectrum of (2) was measured, and it can be seen thatThe excitation spectrum of the product obtained by the preparation scheme of the invention is the same as that reported in the prior literature.
FIG. 20 shows sample Cs 2 ZrCl 6 The yield and the luminous intensity of the sample are changed along with the change of the hydrochloric acid concentration, the trend is very similar to that of the sample 1, the highest yield can reach 95 percent, the hydrochloric acid concentration is shown to have obvious influence on the yield and the luminous intensity of the sample, and the considerable yield and the luminous intensity can be ensured only in concentrated hydrochloric acid.
FIG. 21 shows the sample Cs 2 ZrCl 6 The yield and the luminous intensity of the method are changed along with the addition of the concentrated hydrochloric acid so as to prepare 1mmol of Cs 2 ZrCl 6 For example, the yield and luminescence intensity of the product did not change significantly in the volume range of 0.5-10mL of concentrated hydrochloric acid, which indicates that the volume requirement of concentrated hydrochloric acid in the embodiment of the present invention is relaxed and not strictly limited.
FIG. 22 shows the sample Cs 2 ZrCl 6 The thermal stability test of (a), it can be seen that the sample can maintain around 80% of the initial strength after being heated for 1000 hours at 150 ℃, and excellent thermal stability is shown, which indirectly indicates the reliability of the preparation scheme.
Example 5: perovskite material doping expansion 4 realized by using scheme in the invention
The preparation method comprises the following steps: to prepare 1mmol of Cs 2 Na 0.9 Ag 0.1 InCl 6 10% by weight of CsCl (0.3367 g), naCl (0.9 mmol) (0.0526 g), CH (0.1 mmol) were weighed out 3 COOAg(0.0167g)，1mmol InCl 3 ·4H 2 O (0.2932 g) and 0.1mmol of CrCl 3 (0.0266 g) in a test tube. A small amount of 35wt% concentrated hydrochloric acid (2 mL was used for the particular experiment) was added and the mixture was stirred appropriately for about 1 minute at 0.5W/cm 2 Sonication for about 5 minutes followed by stirring at 8000rpm for about 5 minutes gave a bright luminescent product.
After the preparation is finished, the mixture is centrifuged for 2-3 times at 5000rpm-10s, and then is washed by ethanol, and the final precipitate is put into an oven and dried for about 2 hours at 60 ℃ to obtain a sample in the form of final powder.
And (3) testing conditions are as follows: same as in example 1.
The experimental results are as follows: FIG. 23 shows sample Cs 2 Na 0.9 Ag 0.1 InCl 6 10% XRD test result of Cr, it can be seen that according to the preparation scheme proposed by the present invention, the diffraction peak of the product corresponds to the peak position of the standard card, indicating that the crystal phase of the pure product has been obtained.
FIG. 24 shows sample Cs 2 Na 0.9 Ag 0.1 InCl 6 10% Cr-it can be seen that the sample was able to produce corresponding Cr luminescence in the near infrared region, in agreement with the previous report, indicating that Cr is emitted 3+ Has been successfully incorporated.
Example 6: perovskite material doping expansion 5 realized by the scheme of the invention
The preparation method comprises the following steps: to prepare 1mmol of Cs 2 Na 0.9 Ag 0.1 InCl 6 10% Tb, 2mmol of CsCl (0.3367 g), 0.9mmol of NaCl (0.0526 g), 0.1mmol of AgCl (0.0143 g), 1mmol of InCl 3 ·4H 2 O (0.2932 g) in test tube A. 0.1mmol of TbCl was weighed 3 (0.0264 g) in a test tube and a small amount of ultrapure water (the amount added in the specific experiment herein was 100. Mu.L) was added to dissolve and add to test tube A, a small amount of 35wt% concentrated hydrochloric acid (the amount added in the specific experiment herein was 2 mL) was added to test tube A, and after the mixture was properly stirred for about 1 minute, the mixture was stirred at 0.5W/cm 2 Sonication for about 5 minutes followed by stirring at 8000rpm for about 5 minutes gave a bright luminescent product.
After the preparation is finished, the mixture is centrifuged for 2-3 times at 5000rpm-10s, and then is washed by ethanol, and the final precipitate is put into an oven and dried for about 2 hours at 60 ℃ to obtain a sample in the form of final powder.
And (3) testing conditions: same as in example 1.
The experimental results are as follows: FIG. 25 shows sample Cs 2 Na 0.9 Ag 0.1 InCl 6 10% of the results of the XRD test on Tb, it can be seen that the diffraction peaks of the product correspond to the peak positions of the standard card according to the embodiment proposed by the present invention, indicating that the crystal phases of the target product have been obtained.
FIG. 26 shows the sample Cs 2 Na 0.9 Ag 0.1 InCl 6 10 The results of the Spectrum test on Tb, it can be seen that according to the embodiment proposed by the present invention, the target product which has been obtained exhibits Tb while emitting a broad spectrum of the self-trapping state 3+ The peak emission of (D), as shown at 494,547 and 622nm in the figure, indicates Tb 3+ Successful incorporation of the ions.
Example 7: perovskite material doping expansion 6 realized by using the scheme of the invention
The preparation method comprises the following steps: to prepare 1mmol of Cs 2 Na 0.9 Ag 0.1 InCl 6 10% taking as an example the Tm, 2mmol of CsCl (0.3367 g), 0.9mmol of NaCl (0.0526 g), 0.1mmol of AgCl (0.0143 g), 1mmol of InCl 3 ·4H 2 O (0.2932 g) and 0.1mmol of TmCl 3 ·xH 2 O (0.0275 g) in a test tube. A small amount of 35wt% concentrated hydrochloric acid (2 mL for the particular experiment) was added to the tube and after shaking the mixture for about 1 minute with appropriate stirring, the mixture was shaken at 0.5W/cm 2 And (3) carrying out ultrasonic treatment for about 5 minutes, and stirring at 6000rpm for about 5 minutes to obtain a bright luminous product, and carrying out sample sieve filtration on the product to remove incompletely reacted solid particles.
After the preparation is finished, the mixture is centrifuged for 2-3 times at 5000rpm-10s, and then is washed by ethanol, and the final precipitate is put into an oven and dried for about 2 hours at 60 ℃ to obtain a sample in the form of final powder.
And (3) testing conditions are as follows: same as in example 1.
The experimental results are as follows: FIG. 27 shows the sample Cs 2 Na 0.9 Ag 0.1 InCl 6 10% XRD test result of Tm, it can be seen that the diffraction peak of the product corresponds to the peak position of the standard card according to the proposed embodiment of the present invention, indicating that the crystalline phase of the objective product has been obtained.
FIG. 28 shows sample Cs 2 Na 0.9 Ag 0.1 InCl 6 10% Tm results of spectroscopic test, it can be seen that the target product which has been obtained according to the embodiment proposed by the present invention exhibits Tm 3+ Emission characteristics in the near infrared regionThe Tm is indicated by the 1222nm spike in the figure and the multi-spike emission in the 1400-1550nm band 3+ Successful incorporation of the ions.
Example 8: perovskite material doping expansion 7 achieved by the scheme of the invention
The preparation method comprises the following steps: to prepare 1mmol of Cs 2 ZrCl 6 5% of Sb as an example, 2mmol of CsCl (0.3367 g), 1mmol of ZrCl were weighed 4 (0.2330 g) and 0.025mmol of SbCl 3 (0.0057 g) A test tube was charged with a small amount of 35wt% concentrated hydrochloric acid (2 mL was used in the experiment here), and after stirring the mixture at 3000rpm for about 1 minute, the mixture was stirred at 0.5W/cm 2 And carrying out ultrasonic treatment for 1 minute to obtain a bright luminous product.
After the preparation is finished, the mixture is centrifuged for 2-3 times at 5000rpm-10s, and then is washed by ethanol, and the final precipitate is put into an oven and dried for about 2 hours at 60 ℃ to obtain a sample in the form of final powder.
And (3) testing conditions: same as in example 1.
The experimental results are as follows: FIG. 29 shows sample Cs 2 ZrCl 6 5% XRD test result of Sb, it can be seen that according to the proposed embodiment of the present invention, the diffraction peak of the product corresponds to the peak position of the standard card, indicating that the crystalline phase of the target product has been obtained.
FIG. 30 shows the sample Cs 2 ZrCl 6 5 The results of the spectral test of Sb, it can be seen that Sb is according to the embodiment proposed in the present invention 3+ Corresponding luminescence can be generated, indicating that Sb 3+ Successful incorporation.
Example 9: perovskite material doping expansion 8 realized by using scheme in the invention
The preparation method comprises the following steps: to prepare 1mmol of Cs 2 ZrCl 6 5 percent of Bi as an example, weighing 1mmol of Cs 2 CO 3 (0.3258g)，1mmol ZrCl 4 (0.2330 g) and 0.05mmol of BiCl 3 (0.0158 g) A small amount of 35wt% concentrated hydrochloric acid (2 mL for this particular experiment) was added to the tube and the mixture was stirred at 2000rpm for about 1 minute to give a bright luminescent product.
After the preparation is finished, the mixture is centrifuged for 5000rpm to 10s, then is washed by ethanol for 2 to 3 times, and the final precipitate is put into an oven and is dried for about 2 hours at 60 ℃ to obtain a sample in the form of final powder.
And (3) testing conditions are as follows: same as in example 1.
The experimental results are as follows: FIG. 31 shows the sample Cs 2 ZrCl 6 5% XRD test result of Bi, it can be seen that according to the proposed embodiment of the present invention, the diffraction peak of the product corresponds to the peak position of the standard card, indicating that the crystalline phase of the objective product has been obtained.
FIG. 32 shows sample Cs 2 ZrCl 6 5% Bi from the results of the spectral test, it can be seen that Bi according to the embodiment proposed in the present invention 3+ Can generate corresponding luminescence, which shows that Bi 3+ Successful incorporation.
Example 10: other chloride material expansion is realized by the scheme of the invention 9
The preparation method comprises the following steps: to prepare 1mmol of Cs 2 ZnCl 4 :5％Ce 3+ For example, 2mmol CsCl (0.3367 g), 1mmol ZnCl were weighed 2 (0.1363 g) and 0.05mmol of CeCl 3 (0.0123 g) A small amount of 35wt% concentrated hydrochloric acid (2 mL was used in this particular experiment) was added to the tube, and after stirring the mixture at 3000rpm for about 1 minute, the mixture was stirred at 0.5W/cm 2 And carrying out ultrasonic treatment for 1 minute to obtain a bright luminous product.
After the preparation is finished, the mixture is centrifuged for 2-3 times at 5000rpm-10s, and then is washed by ethanol, and the final precipitate is put into an oven and dried for about 2 hours at 60 ℃ to obtain a sample in the form of final powder.
And (3) testing conditions: same as in example 1.
The experimental results are as follows: FIG. 33 shows sample Cs 2 ZnCl 4 :5％Ce 3+ From the XRD test results, it can be seen that according to the proposed embodiment of the present invention, the diffraction peak of the product corresponds to the peak position of the standard card, indicating that the crystalline phase of the target product has been obtained.
FIG. 34 shows sample Cs 2 ZnCl 4 :5％Ce 3+ The result of the spectral measurement ofTo see the embodiment proposed according to the present invention, ce 3+ Can generate corresponding ultraviolet luminescence to show Ce 3+ Successful incorporation.
It is noted that, if necessary, part of the raw materials in step (1) can be separately dissolved in other solvent (such as water) and then mixed with other raw materials, but the critical initiating solvent for nucleation of the final sample is concentrated hydrochloric acid in step (2), i.e. the specific operation described in example 6, and still falls within the scope of this patent.
The examples mentioned in the present invention only present representative chemical samples, and do not allow the use of this protocol to prepare other chloride samples to evade the scope of protection of the patent.
The core of the preparation scheme provided by the invention is that concentrated hydrochloric acid is added in the step (2) solely, and proper ultrasonic stirring is performed, and on the basis of the addition, fine adjustment of any parameter or additional introduction of any other solvent is included in the protection scope of the invention.
The invention is not the best known technology.
Claims (5)
1. A method for preparing lead-free perovskite luminescent material in batches at room temperature is characterized by comprising the following steps:
(1) Selecting related compounds according to the element composition of the perovskite chemical formula, and preparing materials according to the element proportion;
(2) Adding hydrochloric acid into the above mixture, performing ultrasonic treatment for 1-5min, and stirring at high speed for 1-5min;
wherein, 0.5-10mL of hydrochloric acid is added into each 1mmol of target perovskite; the concentration of hydrochloric acid is 15-35wt%;
(3) And centrifuging the product obtained in the last step, removing supernatant, washing the precipitate with ethanol, and drying to obtain the corresponding perovskite.
2. The method for batch preparation of lead-free perovskite luminescent material at room temperature as claimed in claim 1, wherein the perovskite is Cs 2 ZrCl 6 Or Cs 2 Na 1-x Ag x In 1-y Bi y Cl 6 ，0≤x≤1,0≤y≤1；
Cs 2 ZrCl 6 The compounds related to the perovskite are Cs-containing compounds and Zr-containing compounds;
Cs 2 Na 1-x Ag x In 1-y Bi y Cl 6 the perovskite related compounds are Na-containing compounds, in-containing compounds, bi-containing compounds, cs-containing compounds and Ag-containing compounds;
the various compounds described are all non-oxides.
3. The Cs-containing compound is CsCl or Cs 2 CO 3 ；
The Zr-containing compound is ZrCl 4 Or Zr (CO) 3 ) 2 ；
The Ag-containing compound is AgCl or CH 3 COOAg；
The Na-containing compound is NaCl or NaHCO 3 Or Na 2 CO 3 ；
The In-containing compound is InCl 3 Or In (CH) 3 COO) 3 ；
The Bi-containing compound is BiCl 3 Or Bi (CH) 3 COO) 3 。
4. The method for batch preparation of lead-free perovskite luminescent material at room temperature as claimed in claim 1, characterized in that the rotation speed of the high speed stirring is 1000-8000rpm.
5. The method for batch preparation of lead-free perovskite luminescent material at room temperature as claimed in claim 1, wherein in step (2), after adding hydrochloric acid and before ultrasonic treatment, shaking is further performed.
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