Aramid fiber composite luminescent material containing cesium tin halide perovskite and preparation method thereof

Abstract

The application discloses a cesium tin halide perovskite aramid fiber composite light-emitting material and a preparation method thereof. The method comprises the following steps: 1, preparing a halogen solution; 2, preparing a perovskite precursor solution; 3, heating and stirring the obtained precursor solution and the halogen solution to synthesize, by adjusting the reaction time and the doping concentration, a product with different light-emitting intensities. The method is simple and easy to operate and has low cost. The modified perovskite crystal has good light-emitting performance, and the optical performance and stability are improved. Then, the perovskite crystal with high light-emitting intensity is compounded with aramid / polyphenylene sulfide fiber composite paper (ACFs / PPS), and the composite fiber paper has fluorescent properties and can be used in the fields of fluorescent anti-counterfeiting and intelligent wearable devices. The preparation method is simple and easy to operate and has low cost.

Description

Technical Field

[0001] This invention relates to the field of nanomaterials technology, and in particular to a cesium tin halide perovskite and aramid fiber composite luminescent material and its preparation method. Background Technology

[0002] Perovskites are photoluminescent materials with excellent optical properties. However, cesium lead halide perovskites contain lead, which is toxic and has poor air stability, hindering their large-scale commercial application. Cesium tin halide perovskites, on the other hand, do not contain heavy metals and have strong air stability, making them a promising alternative to cesium lead halide perovskites. However, while cesium tin halide perovskites possess a direct band gap, they lack fluorescence properties. Therefore, modifying cesium tin halide perovskites is crucial for improving their fluorescence performance.

[0003] Meanwhile, the research and application of smart textiles have gradually attracted widespread attention. One of the important raw materials for smart textiles is luminescent fiber. Therefore, using modified cesium tin halide perovskite to composite high-performance fibers to prepare luminescent fibers for applications such as fluorescent anti-counterfeiting and smart textiles is currently one of the research hotspots.

[0004] In the prior art, there are various methods for preparing perovskite. Among them, patent application CN114836194A discloses a method for preparing perovskite, specifically including S1, according to the chemical formula Cs2SnCl6:xBi 3+ ,yTe 4+ The molar ratios of each element were used to prepare cesium, tin, bismuth, and tellurium sources; where x represents the Bi dopant. 3+ The mole fraction, y is the Te doping. 4+ The mole fractions of the tin, bismuth, and tellurium sources are 0 ≤ x ≤ 1 and 0 ≤ y ≤ 1, and x and y are not simultaneously 0; S2, the tin source, bismuth source, and tellurium source are added to a hydrochloric acid solution, mixed, and heated until clear to obtain a first product; S3, a cesium source is added to the first product, stirred and heated for a certain time to obtain a second product; the second product is cooled, the supernatant is removed, and dried to obtain a third product; S4, the third product is added to a mixed solution of silicon source and ethanol, mixed, and hydrochloric acid is added to initiate a polymerization reaction to obtain a polymer product; the polymer product is dried and ground to obtain a silica-coated double perovskite phosphor. This scheme discloses a traditional perovskite preparation process, but for the performance of perovskite, the ratio of raw materials and the reaction process conditions in the preparation method will have a significant impact on the final performance of the perovskite.

[0005] Specifically, the modification methods for cesium tin halide perovskite crystals typically require special reactor vessels to maintain high pressure and high temperature. At the same time, although the cesium tin halide perovskite crystals prepared by existing technologies have a direct band gap, they are difficult to luminesce under ultraviolet light. Therefore, finding a cesium tin halide perovskite crystal that can luminesce under ultraviolet light and applying it to anti-counterfeiting or smart textile materials can further improve the performance requirements of textile materials. Summary of the Invention

[0006] To address the aforementioned problems, one objective of this invention is to provide a metal ion exchange method for modifying cesium tin halide perovskite crystals, which, despite having a direct band gap, are difficult to luminesce under ultraviolet light. The cesium tin halide perovskite crystals prepared by this method exhibit luminescence under ultraviolet light irradiation.

[0007] Furthermore, the present invention is based on the idea of ​​using tellurium tetrachloride to provide tellurium ions for metal ion exchange reaction to adjust the cesium tin halide perovskite crystals, so that the prepared perovskite has good ultraviolet luminescence properties.

[0008] Furthermore, the present invention also involves preparing cesium tin halide perovskite crystals with different luminescence intensities by controlling the doping ratio of tellurium tetrachloride.

[0009] Furthermore, the present invention also involves using the prepared cesium tin halide perovskite crystals with ultraviolet luminescence properties to prepare aramid / polyphenylene sulfide fiber composite sheets, thereby obtaining an aramid / polyphenylene sulfide fiber composite sheet with ultraviolet luminescence.

[0010] Specifically, the present invention addresses the above-mentioned technical problems by providing the following solutions:

[0011] A method for preparing cesium tin halide perovskite includes the following steps:

[0012] Step 1: Preparation of halogen solution

[0013] Hydrochloric acid solution is added to an alcohol solution, followed by tin dichloride and tellurium tetrachloride solid powder, and stirred to dissolve, thus obtaining a halogen solution;

[0014] The melting temperature is 70℃-90℃, preferably 80-90℃.

[0015] In some embodiments, the mass ratio of tin dichloride to tellurium tetrachloride is 10-20:1-4; preferably 10-15:1-2; and more preferably 15-20:2-4.

[0016] In some embodiments, in step 1, the mass ratio of alcohol, hydrochloric acid, tin dichloride and tellurium tetrachloride is 10-20:2-4:50-100:5-20; preferably, the mass ratio is 10-18:2-4:70-100:10-20.

[0017] In some embodiments, in step 1, the amounts of alcohol, hydrochloric acid, tin dichloride, and tellurium tetrachloride are 10-20 mL, 2-4 mL, 50-100 mg, and 5-20 mg, respectively.

[0018] Step 2: Prepare perovskite precursor

[0019] Add cesium carbonate solid powder to hydrochloric acid solution and stir until completely dissolved to obtain perovskite precursor solution;

[0020] The melting temperature is 70℃-90℃, preferably 80-90℃.

[0021] In some embodiments, in step 2, the mass ratio of hydrochloric acid to cesium carbonate is 1-3:100-200, and the preferred mass ratio is 2-3:150-200.

[0022] In some embodiments, in step 2, the amounts of hydrochloric acid and cesium carbonate used are 1-3 mL and 100-200 mg, respectively.

[0023] Step 3: Reaction of halogen solution with pre-perovskite precursor

[0024] The perovskite precursor solution from step 2 was injected into the halogen solution from step 1, and the mixture was heated and stirred to obtain a cesium tin halide perovskite crystal solution.

[0025] In some embodiments, the reaction is heated and stirred, followed by cooling, centrifugation for purification, and dispersion.

[0026] In some embodiments, the perovskite precursor solution in step 2 is 1-5 / 110-130 of the halogen solution in step 1; preferably 2-5 / 120-130.

[0027] In some embodiments, the amount of perovskite precursor solution added in step 3 is 1-3 mL.

[0028] In some embodiments, the reaction time in step 3 is 1-60 min, preferably 5-30 min; more preferably 20-40 min.

[0029] In some embodiments, the solvents used in the centrifugal purification step 3 are ethyl acetate and n-hexane;

[0030] In some embodiments, the centrifugation speed in step 3 is greater than 5000 rpm, preferably greater than 6000 rpm; and the centrifugation time is greater than 4 min, preferably greater than 6 min.

[0031] In addition, this disclosure also provides a method for preparing aramid / polyphenylene sulfide fiber composite sheets (ACFs / PPS) using cesium tin halide perovskite prepared by the above method;

[0032] The aforementioned aramid / polyphenylene sulfide fiber composite sheet (ACFs / PPS) has fluorescent properties;

[0033] The composite sheet (ACFs / PPS) exhibits a color reaction under ultraviolet light and can maintain its fluorescence in air for a long time.

[0034] More specifically, in some embodiments, this disclosure provides a method for preparing aramid / polyphenylene sulfide fiber composite sheets using cesium tin halide perovskite prepared by the above method, comprising the following steps:

[0035] Step A: Impregnate the sheet with the cesium tin halide perovskite crystal solution prepared by the aforementioned scheme;

[0036] The sheet material is an impregnated aramid / polyphenylene sulfide fiber composite sheet (ACFs / PPS).

[0037] Step B: Dry the composite sheet impregnated in Step A to obtain a perovskite crystal fiber composite sheet with fluorescent properties.

[0038] In addition, in some embodiments, this disclosure provides a cesium tin halide perovskite and aramid fiber composite light-emitting sheet, wherein the substrate of the composite light-emitting sheet is an aramid / polyphenylene sulfide fiber composite sheet (ACFs / PPS).

[0039] The luminescent material is a cesium tin halide perovskite crystal;

[0040] The cesium tin halide perovskite crystals are obtained by a metal ion exchange reaction using tellurium tetrachloride as a donor, and exhibit luminescence under ultraviolet light irradiation.

[0041] The beneficial effects of the present invention are as follows: 1. The high-performance cesium tin halide perovskite crystal modification method provided by the present invention is carried out under normal pressure conditions, without the participation of heavy metals and special organic solvents in the reaction, and is an environmentally friendly modification method.

[0042] 2. The perovskite preparation method provided by this invention is simple, low-cost, and the generated products can be fully utilized with a high yield.

[0043] 3. Using the modification method for high-performance cesium tin halide perovskite crystals provided by this invention, cesium tin halide perovskite crystals with different luminescence intensities are prepared by controlling the doping ratio of tellurium tetrachloride. Through modification, the original morphology and size are retained, and their fluorescence performance and stability are improved. Simultaneously, the fluorescent anti-counterfeiting paper formed by combining perovskite crystals and fiber paper has certain fluorescent properties, exhibits a color reaction under ultraviolet light, and can maintain its fluorescent properties in air for a long time. Attached Figure Description

[0044] Figure 1 Scanning electron microscope image of the cesium tin halide perovskite crystals prepared in Example 3;

[0045] Figure 2 Comparison of fluorescence properties of perovskite crystals obtained in Examples 1-2;

[0046] Figure 3 Comparison of fluorescence properties of perovskite crystal composite sheets before and after modification in Example 3;

[0047] Figure 4 Comparison of fluorescence of the perovskite crystal composite sheet obtained in Example 3 before and after modification under ultraviolet light;

[0048] Figure 5 The stability of the modified perovskite crystal composite sheet obtained in Example 3 in air. Detailed Implementation

[0049] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0050] Example 1

[0051] A cesium tin halide perovskite luminescent material and its preparation method, comprising the following steps:

[0052] Step 1: Preparation of halogen solution

[0053] 15 mL of ethanol, 3 mL of hydrochloric acid, and 90 mg of tin dichloride were placed in a three-necked flask. The flask was heated and stirred at 80 °C until the tin dichloride was completely dissolved, yielding a halogen solution.

[0054] Step 2: Preparation of perovskite precursor solution

[0055] 2 mL of hydrochloric acid and 180 mg of cesium carbonate were placed in a three-necked flask. The flask was heated and stirred at 80 °C until the cesium carbonate was completely dissolved, yielding a perovskite precursor solution.

[0056] Step 3: Quickly inject 3 mL of the perovskite precursor solution from Step 2 into the halogen solution from Step 1. React at 80°C with stirring for 50 minutes. After the reaction is complete, cool to 40°C and centrifuge at 6000 rpm for 5 minutes to purify. Discard the supernatant, add n-hexane and ethyl acetate to the solid precipitate, and centrifuge at 6000 rpm for 5 minutes to purify. Repeat twice. Then disperse the solid precipitate in 10 mL of n-hexane to obtain a cesium tin halide perovskite crystal solution.

[0057] Example 2

[0058] A cesium tin halide perovskite luminescent material and its preparation method, comprising the following steps:

[0059] Step 1: Preparation of halogen solution

[0060] 15 mL of ethanol, 3 mL of hydrochloric acid, 90 mg of tin dichloride, and 5 mg of tellurium tetrachloride were placed in a three-necked flask. The flask was heated and stirred at 80 °C until the tin dichloride and tellurium tetrachloride were completely dissolved, yielding a halogen solution.

[0061] Step 2: Preparation of perovskite precursor solution

[0062] 2 mL of hydrochloric acid and 180 mg of cesium carbonate were placed in a three-necked flask. The flask was heated and stirred at 80 °C until the cesium carbonate was completely dissolved, yielding a perovskite precursor solution.

[0063] Step 3: Quickly inject 3 mL of the perovskite precursor solution from Step 2 into the halogen solution from Step 1. React at 80°C with stirring for 60 minutes. After the reaction is complete, cool to 40°C and centrifuge at 6000 rpm for 5 minutes to purify. Discard the supernatant, add n-hexane and ethyl acetate to the solid precipitate, and centrifuge at 6000 rpm for 5 minutes to purify. Repeat twice. Then disperse the solid precipitate in 10 mL of n-hexane to obtain a cesium tin halide perovskite crystal solution.

[0064] Example 3

[0065] A cesium tin halide perovskite-aramid fiber composite luminescent material and its preparation method include the following steps:

[0066] Step 1: Preparation of halogen solution

[0067] 15 mL of ethanol, 3 mL of hydrochloric acid, 90 mg of tin dichloride, and 13 mg of tellurium tetrachloride were placed in a three-necked flask. The flask was heated and stirred at 80 °C to completely dissolve the tin dichloride and tellurium tetrachloride, thus obtaining a halogen solution.

[0068] Step 2: Preparation of perovskite precursor solution

[0069] 2 mL of hydrochloric acid and 180 mg of cesium carbonate were placed in a three-necked flask. The flask was heated and stirred at 80 °C until the cesium carbonate was completely dissolved, yielding a perovskite precursor solution.

[0070] Step 3: Quickly inject 3 mL of the perovskite precursor solution from Step 2 into the halogen solution from Step 1. React at 80°C with stirring for 60 minutes. After the reaction is complete, cool to 40°C and centrifuge at 6000 rpm for 5 minutes to purify. Discard the supernatant, add n-hexane and ethyl acetate to the solid precipitate, and centrifuge at 6000 rpm for 5 minutes to purify. Repeat twice. Then disperse the solid precipitate in 10 mL of n-hexane to obtain a cesium tin halide perovskite crystal solution.

[0071] Step 4: Use the cesium tin halide perovskite crystal solution obtained in Step 3 to soak aramid / polyphenylene sulfide fiber composite paper (ACFs / PPS), and then dry it to obtain perovskite crystal fiber composite paper with fluorescent properties.

[0072] Results analysis:

[0073] Figure 1 The image shows the appearance of the cesium tin halide perovskite crystals in Example 3. The scanning electron microscope image shows that the perovskite crystals have regular morphology, uniform size distribution, good nanocrystal morphology, and regular arrangement.

[0074] Figure 2 The image shows a comparison of the fluorescence properties of perovskite crystals before and after modification. Specifically, the perovskite prepared in Examples 1-3 was tested for fluorescence properties. It can be found that the modified cesium tin halide perovskite crystals have certain fluorescence properties, and the fluorescence properties of 13 mL tellurium tetrachloride (Example 3) are better than those of 3 mL tellurium tetrachloride (Example 2).

[0075] Figure 3 The image shows a comparison of the fluorescence properties of the perovskite crystal composite paper before and after modification (Example 3). It can be seen that the modified perovskite crystal composite paper possesses certain fluorescence properties.

[0076] Figure 4 The image shows a fluorescence comparison of the perovskite crystal composite sheet before and after modification under ultraviolet light. It can be observed that the modified composite sheet appears yellow under ultraviolet light.

[0077] Figure 5 The image shows the stability of the modified perovskite crystal composite paper in air. It can be seen that the modified composite paper can maintain its fluorescent properties for a long time in air, and still has good fluorescent performance after 4500 hours.

[0078] In summary, compared to the perovskite crystals of Example 1, the perovskite crystals of Example 2 incorporated an appropriate amount of tellurium tetrachloride. This modification method utilizes tellurium tetrachloride to provide tellurium ions for metal ion exchange reactions, adjusting the band gap in its structure and enhancing its fluorescence performance. Meanwhile, in Example 3, the modified cesium tin halide perovskite crystal solution was used to soak aramid / polyphenylene sulfide fiber composite paper (ACFs / PPS), followed by drying, to obtain perovskite crystal fiber composite paper with fluorescent properties.

[0079] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A aramid fiber composite luminescent sheet containing cesium tin halide perovskite, characterized in that, The substrate of the aramid fiber composite luminescent sheet is an aramid / polyphenylene sulfide fiber composite sheet (ACFs / PPS); The fluorescent component of the aramid fiber composite luminescent sheet is a cesium tin halide perovskite crystal. The cesium tin halide perovskite crystals are prepared by reacting a perovskite precursor solution with a halogen solution containing tellurium tetrachloride. The preparation method of cesium tin halide perovskite crystals is as follows: Step 1: Preparation of halogen solution Add hydrochloric acid solution to an alcohol solution, then add tin dichloride and tellurium tetrachloride solid powder, and stir until completely dissolved to obtain a halogen solution; Step 2: Prepare the precursor. Add cesium carbonate solid powder to hydrochloric acid solution and stir until completely dissolved to obtain perovskite precursor solution; Step 3: Preparation of cesium tin halide perovskite crystal solution The perovskite precursor solution from step 2 was rapidly injected into the halogen solution from step 1, and the reaction was carried out under heating and stirring conditions. After the reaction was completed, the solution was cooled, centrifuged, purified, and dispersed to obtain a cesium tin halide perovskite crystal solution. in, In step 1, the mass ratio of tin dichloride to tellurium tetrachloride in the preparation of the halogen solution is 15-20:2-4; In step 3, the ratio of the perovskite precursor solution from step 2 to the halogen solution from step 1 is 1-5:110-130.

2. The aramid fiber composite luminescent sheet containing cesium tin halide perovskite according to claim 1, characterized in that, The aramid fiber composite luminescent sheet appears yellow under ultraviolet light.

3. A method for preparing an aramid fiber composite luminescent sheet containing cesium tin halide perovskite as described in any one of claims 1-2, characterized in that, Step 1: Preparation of halogen solution Add hydrochloric acid solution to an alcohol solution, then add tin dichloride and tellurium tetrachloride solid powder, and stir until completely dissolved to obtain a halogen solution; Step 2: Prepare the precursor. Add cesium carbonate solid powder to hydrochloric acid solution and stir until completely dissolved to obtain perovskite precursor solution; Step 3: Preparation of cesium tin halide perovskite crystal solution The perovskite precursor solution from step 2 was rapidly injected into the halogen solution from step 1, and the reaction was carried out under heating and stirring conditions. After the reaction was completed, the solution was cooled, centrifuged, purified, and dispersed to obtain a cesium tin halide perovskite crystal solution. Step 4: Prepare aramid fiber composite luminescent sheet containing cesium tin halide perovskite. The cesium tin halide perovskite crystal solution obtained in step 3 was used to soak aramid / polyphenylene sulfide fiber composite sheets (ACFs / PPS), and then dried to obtain aramid fiber composite light-emitting sheets containing cesium tin halide perovskite.

4. The method for preparing the aramid fiber composite luminescent sheet containing cesium tin halide perovskite as described in claim 3, characterized in that, The stirring temperature in steps 1 and 2 is 80-90℃.

5. The method for preparing the aramid fiber composite luminescent sheet containing cesium tin halide perovskite as described in claim 4, characterized in that, In step 1, the mass ratio of tin dichloride to tellurium tetrachloride is 15-20:2-4.

6. The method for preparing the aramid fiber composite luminescent sheet containing cesium tin halide perovskite as described in claim 4, characterized in that, In step 1, the mass ratio of alcohol, hydrochloric acid, tin dichloride, and tellurium tetrachloride is 10-18:2-4:70-100:10-20.

7. The method for preparing the aramid fiber composite luminescent sheet containing cesium tin halide perovskite as described in claim 3, characterized in that, In step 2, the mass ratio of hydrochloric acid to cesium carbonate is 1-3:100-200.

8. The method for preparing the aramid fiber composite luminescent sheet containing cesium tin halide perovskite as described in claim 3, characterized in that, In step 3, the ratio of the perovskite precursor solution from step 2 to the halogen solution from step 1 is 1-5:110-130.

9. The method for preparing the aramid fiber composite luminescent sheet containing cesium tin halide perovskite as described in claim 3, characterized in that, The reaction time in step 3 is 20-40 minutes.

10. The method for preparing the aramid fiber composite luminescent sheet containing cesium tin halide perovskite as described in claim 4, characterized in that, The solvents used in the centrifugal purification process of step 3 are ethyl acetate and n-hexane.

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