A doped high-chlorate modified anti-perovskite material, a preparation method thereof and application thereof

Abstract

The application discloses a kind of anti-perovskite materials. Specifically, a kind of doping perchlorate modified anti-perovskite material, its preparation method and application are provided. The anti-perovskite material has high quantum luminescence efficiency, has wide application prospect in the field of optoelectronics, and its conductivity is high, has wide application prospect in the solid-state electrolyte material of solid-state lithium battery.

Description

Technical Field

[0001] This invention relates to the fields of electrolyte materials and optoelectronic materials for solid-state lithium batteries, specifically to an anti-perovskite material modified with perchlorate, its preparation method, and its applications. Background Technology

[0002] The general structural formula of anti-perovskite materials can be written as X'3A'B', which is the opposite of perovskite. Here, the X' position is usually a monovalent cation; the A' position is usually a monovalent anion; and the B' position is usually a divalent anion. The positions of the cation and anion in the crystal structure are reversed in both anti-perovskite and perovskite structures.

[0003] Thanks to their similar structure to perovskites, anti-perovskite materials have wide applications in various fields such as magnetism, photoelectric detection (Nature Photonics 2024, 18, 990–997), ferroelectricity (Angew. Chem. Int. Ed. 2018, 57, 11939-11942), superconductivity, catalysis, and solid-state batteries. Especially in the field of solid-state batteries, anti-perovskite materials have attracted much attention from researchers because they have high operating voltage, do not react with the negative electrode, have high conductivity at room temperature, and low synthesis cost, making them suitable as solid electrolyte materials for lithium batteries.

[0004] Additionally, it is worth noting that recent research has shown a class of anti-perovskite materials, Cs3MX5 (X = Cl). - , Br - and I - It also exhibits excellent luminescent properties and has been successfully used to fabricate the first anti-perovskite light-emitting diode, with a maximum external quantum efficiency of up to 12.5% ​​and a maximum luminance of up to 3990 cd / m². -2 (ACS Energy Lett. 2021, 6, 1901-1911).

[0005] Therefore, anti-perovskite materials have wide applications in solid-state electrolyte materials and optoelectronic materials for solid-state lithium batteries. Further exploration of new anti-perovskite materials therefore has significant commercial value. Summary of the Invention

[0006] The technical problem this invention aims to solve is that anti-perovskite materials are not yet widely used in solid-state batteries and optoelectronic materials. Therefore, this invention provides a perchlorate-doped modified anti-perovskite material... Its preparation method and its application. This anti-perovskite material exhibits high quantum luminescence efficiency, which is significant for applications in optoelectronics. It has broad application prospects in the field, and its high conductivity makes it a promising candidate for use in solid electrolytes for solid-state lithium batteries.

[0007] The present invention provides an anti-perovskite material with the following general molecular formula A3B(ClO4) n X 5-n ;

[0008] where 0 < n < 5; A is a monovalent cation; B is a divalent cation; X is a monovalent anion.

[0009] In the present invention, A is one or more of cesium ion, rubidium ion, potassium ion, sodium ion, lithium ion, methylamine cation, and formamidine cation.

[0010] In the present invention, A is cesium ion.

[0011] In the present invention, B is manganese ion (Mn 2+ ), zinc ion (Zn 2+ ), lead ion (Pb 2+ ), or tin ion (Sn 2+ ), platinum ion (Pt 2+ ), nickel ion (Ni 2+ ), palladium ion (Pd 2+ ).

[0012] In the present invention, B is manganese ion (Mn 2+ ).

[0013] In the present invention, X is F - , Cl - , Br - , or I - .

[0014] In the present invention, X is Br - .

[0015] In the present invention, the general molecular formula of the anti-perovskite material is Cs3Mn(ClO4) n X 5-n .

[0016] In the present invention, the general molecular formula of the anti-perovskite material is Cs3Mn(ClO4) n Br 5-n .

[0017] In the present invention, n is 0.1 - 1; for example, 0.1, 0.3, 0.5, 0.7, 0.9, or 1.

[0018] In the present invention, the perovskite material is prepared by the following preparation method:

[0019] (4) Weigh the materials AX, BX2, and XClO4 according to the molar ratio of the general molecular formula A3B(ClO4) n X 5-n ;

[0020] (5) Dissolve the above materials in a solvent, and then heat and stir to obtain an anti-perovskite precursor solution;

[0021] (6) The above anti-perovskite precursor solution is slowly heated to volatilize, causing it to crystallize and precipitate, and then dried to obtain the anti-perovskite material;

[0022] Wherein, X, A, and B are as defined above.

[0023] In this invention, AX is CsBr.

[0024] In this invention, BX2 is MnBr2.

[0025] In this invention, XClO4 is CsClO4.

[0026] In this invention, in step (2), the solvent is water and / or an alcohol solvent.

[0027] In this invention, in step (2), when the solvent is an alcohol solvent, the alcohol solvent is... Methanol and / or ethanol.

[0028] In this invention, in step (2), the heating and stirring time is 0.1-12 hours.

[0029] In this invention, in step (2), the temperature of heating and stirring is 20-60℃.

[0030] The present invention also provides an application of the above-mentioned anti-perovskite material in "X-ray scintillator imaging".

[0031] The present invention also provides an application of the above-mentioned anti-perovskite material in the field of new energy vehicles.

[0032] The present invention also provides an application of the above-mentioned anti-perovskite material as a solid electrolyte in lithium batteries.

[0033] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0034] The reagents and raw materials used in this invention are all commercially available.

[0035] The positive and progressive effects of this invention are as follows: This invention provides an anti-perovskite material with excellent quantum luminescence efficiency, which has broad application prospects in the optoelectronic field, and its high conductivity also makes it a promising candidate for use in solid electrolytes of solid-state lithium batteries. Attached Figure Description

[0036] Figure 1 This is a photograph of anti-perovskite material 2 in its ground state.

[0037] Figure 2 This is a photograph of anti-perovskite material 2 under light excitation at a wavelength of 365 nm.

[0038] Figure 3 The excitation spectrum of anti-perovskite material 2 is shown.

[0039] Figure 4 The fluorescence emission spectrum of anti-perovskite material 2 under 365 nm excitation is shown.

[0040] Figure 5 The excitation spectrum of anti-perovskite material 6 is shown.

[0041] Figure 6 The fluorescence emission spectrum of anti-perovskite material 6 under 365 nm excitation.

[0042] Figure 7 The excitation spectrum of anti-perovskite material 7 is shown.

[0043] Figure 8 The fluorescence emission spectrum of anti-perovskite material 7 under 365 nm excitation is shown. Detailed Implementation

[0044] The present invention will be further illustrated by means of embodiments below, but this does not limit the present invention to specific embodiments. Within the scope of the embodiments described. Experimental methods in the following embodiments that do not specify specific conditions are performed according to conventional methods and conditions, or as selected according to the product instructions.

[0045] Example 1

[0046] The anti-perovskite precursor solution was prepared by dissolving CsBr:MnBr2:CsClO4 in 5 mL of H2O at a molar ratio of 2.9:1:0.1, where MnBr2 was 0.05 mmol (10.74 mg), CsBr was 0.145 mmol (30.86 mg), and CsClO4 was 0.005 mmol (1.16 mg). The solution was stirred and heated at 50 °C for 12 h to prepare the anti-perovskite precursor solution. The solution was then slowly heated at 55 °C to volatilize the precursor, allowing it to slowly crystallize and precipitate. Finally, the solution was dried to obtain anti-perovskite material 1.

[0047] Example 2

[0048] The anti-perovskite precursor solution was prepared by dissolving CsBr:MnBr2:CsClO4 in 5 mL of H2O at a molar ratio of 2.7:1:0.3, where MnBr2 was 0.05 mmol (10.74 mg), CsBr2 was 0.135 mmol (28.73 mg), and CsClO4 was 0.015 mmol (3.49 mg). The solution was stirred and heated at 50 °C for 12 h to prepare the anti-perovskite precursor solution. The solution was then slowly heated at 55 °C to volatilize the precursor, allowing it to slowly crystallize and precipitate. Finally, the precipitate was dried to obtain anti-perovskite material 1.

[0049] Example 3

[0050] The anti-perovskite precursor solution was prepared by dissolving CsBr:MnBr2:CsClO4 in 5 mL of H2O at a molar ratio of 2.5:1:0.5, where MnBr2 was 0.05 mmol (10.74 mg), CsBr was 0.125 mmol (26.60 mg), and CsClO4 was 0.025 mmol (5.80 mg). The solution was stirred and heated at 50 °C for 12 h to prepare the anti-perovskite precursor solution. The solution was then slowly heated at 55 °C to volatilize the precursor, allowing it to slowly crystallize and precipitate. Finally, the solution was dried to obtain anti-perovskite material 1.

[0051] Example 4

[0052] The anti-perovskite precursor solution was prepared by dissolving CsBr:MnBr2:CsClO4 in 5 mL of H2O at a molar ratio of 2.3:1:0.7, where MnBr2 was 0.05 mmol (10.74 mg), CsBr was 0.115 mmol (24.47 mg), and CsClO4 was 0.035 mmol (8.13 mg). The solution was stirred and heated at 50 °C for 12 h to prepare the anti-perovskite precursor solution. The solution was then slowly heated at 55 °C to volatilize the precursor, allowing it to slowly crystallize and precipitate. Finally, the solution was dried to obtain anti-perovskite material 4.

[0053] Example 5

[0054] The anti-perovskite precursor solution was prepared by dissolving CsBr:MnBr2:CsClO4 in 5 mL of H2O at a molar ratio of 2.1:1:0.9, where MnBr2 was 0.05 mmol (10.74 mg), CsBr was 0.105 mmol (22.35 mg), and CsClO4 was 0.045 mmol (10.46 mg). The solution was stirred and heated at 50 °C for 12 h to prepare the anti-perovskite precursor solution. Subsequently, the anti-perovskite precursor solution was slowly heated at 55 °C to volatilize, allowing it to slowly crystallize and precipitate. Finally, it was dried to obtain anti-perovskite material 5.

[0055] Example 6

[0056] The anti-perovskite precursor solution was prepared by dissolving CsBr:MnBr2:CsClO4 in 5 mL of H2O at a molar ratio of 2:1:1, where MnBr2 was 0.05 mmol (10.74 mg), CsBr was 0.1 mmol (21.28 mg), and CsClO4 was 0.05 mmol (11.62 mg). The solution was stirred and heated at 50 °C for 12 h to prepare the anti-perovskite precursor solution. The solution was then slowly heated at 55 °C to volatilize the precursor, allowing it to slowly crystallize and precipitate. Finally, the solution was dried to obtain anti-perovskite material 6.

[0057] Comparative Example 1

[0058] The anti-perovskite precursor solution was prepared by dissolving CsBr:MnBr2 in 5 mL of H2O at a molar ratio of 3:1, with MnBr2 at 0.05 mmol (10.74 mg) and CsBr at 0.15 mmol (31.92 mg). The solution was stirred and heated at 50 °C for 12 h to obtain the anti-perovskite precursor solution. The perovskite precursor solution was then slowly heated at 55 °C to volatilize and allow it to slowly crystallize out. Finally, the solution was dried to obtain the anti-perovskite material 7.

[0059] Example 1

[0060] Photophysical testing

[0061] The anti-perovskite materials of Examples 1-6 and Comparative Example 1 of the present invention were tested for their excitation spectra, emission spectra, and quantum yields using an Edinburgh analytical instrument (FLS980 fluorescence spectrometer). The quantum yields were determined using an Edinburgh FLS980 spectrophotometer in an integrating sphere with a diameter of 142 mm.

[0062] Experimental Procedure: The xenon lamp light source was turned on and preheated for 30 minutes, while the fluorescence spectrometer detector was cooled to -20°C. At room temperature, the solid product was thoroughly ground into a uniform powder to prevent particle agglomeration from affecting test uniformity. The sample was fixed in a solid sample holder, ensuring the test surface was aligned with the test light source. Subsequently, ultraviolet light with a wavelength of 365 nm was used for excitation, and the test sample exhibited green fluorescence emission at 518 nm.

[0063] Among them, the excitation spectrum of anti-perovskite material 2 is as follows: Figure 3 As shown, the fluorescence emission spectrum of anti-perovskite material 2 is as follows: Figure 4 As shown; the excitation spectrum of anti-perovskite material 6 is as follows. Figure 5 As shown, the fluorescence emission spectrum of anti-perovskite material 6 is as follows: Figure 6 As shown; the excitation spectrum of anti-perovskite material 7 is as follows. Figure 5 As shown, the fluorescence emission spectrum of anti-perovskite material 6 is as follows: Figure 7 As shown in the figure. The specific experimental results are shown in Table 1.

[0064] Table 1

[0065] Material Maximum emission wavelength Quantum yield Anti-perovskite materials 1 516nm / Anti-perovskite materials 2 516nm 72.1％ Anti-perovskite materials 3 516nm / Anti-perovskite materials 4 516nm / Anti-perovskite materials 5 516nm / Anti-perovskite materials 6 516nm 51.4％ Anti-perovskite materials 7 515nm 29.6％

[0066] Results and Discussion: As shown in the table above, although the maximum emission wavelength hardly shifted after adding CsSCN, the external quantum efficiency of the anti-perovskite material was significantly increased from 29.6% to over 51.8%. It is evident that its luminescence efficiency was significantly improved, which was unexpected by those skilled in the art. Therefore, this is an anti-perovskite material with excellent performance.

[0067] 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 scope of protection of the present invention.

Claims

1. An anti-perovskite material, characterized in that, It has the following general molecular formula: A3B(ClO4) n X 5-n ;in; 0 < n < 5; A is cesium ion; B is Mn 2+ ; X is a monovalent anion.

2. The anti-perovskite material as described in claim 1, characterized in that, The general molecular formula of the anti-perovskite material is Cs3Mn(ClO4). n Br 5-n .

3. The anti-perovskite material as described in claim 1, characterized in that, n is between 0.1 and 1.

4. The anti-perovskite material as described in claim 3, characterized in that, n is 0.1, 0.3, 0.5, 0.7, 0.9 or 1.

5. A method for preparing the anti-perovskite material as described in claim 1, characterized in that, It is prepared through the following steps: (1) Mix materials AX, BX2 and AC1O4 according to the general molecular formula A3B(ClO4). n X 5-n Compare and weigh; (2) Dissolve the above materials in a solvent, and then heat and stir to obtain an anti-perovskite precursor solution; (3) The above anti-perovskite precursor solution is slowly heated to volatilize, causing it to crystallize and precipitate, and then dried to obtain the anti-perovskite material; Wherein, n, X, A and B are as defined in claim 1.

6. The method for preparing the anti-perovskite material as described in claim 5, characterized in that, It meets one or more of the following conditions: (1) AX is CsBr; (2) BX2 is MnBr2; (3) AClO4 is CsClO4; (4) In step (2), the solvent is water and / or an alcohol solvent; (5) In step (2), when the solvent is an alcohol solvent, the alcohol solvent is methanol and / or ethanol; (6) In step (2), the heating and stirring time is 0.1-12 hours; (7) In step (2), the temperature of heating and stirring is 20-60℃.

7. The application of an anti-perovskite material as described in any one of claims 1-4 in X-ray scintillator imaging, or its application as a solid electrolyte in lithium batteries.

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