Fluorine lithium salt phosphorescent material and preparation method thereof

Abstract

The invention discloses a fluorine lithium acid salt phosphorescent material and a preparation method thereof. The chemical composition of the fluorine lithium acid salt phosphorescent material is Ba (1-x) Li (1-2x) F3: xMn < 4 + >, wherein x is the mole percentage coefficient of the doped ion Mn < 4 + > relative to the monovalent lithium ion, 0 lt; x is less than or equal to 5%. The lithium fluoride phosphorescent material can be effectively excited by ultraviolet light, near ultraviolet light and blue light, and emits high-color-purity narrow-band red light of 640 nm. The lithium fluoride phosphorescent material provided by the invention has a large CIE-x value, short fluorescence lifetime and excellent chemical stability, and can effectively expand the color gamut of LED backlight.

Description

Technical Field

[0001] The present invention belongs to the technical field of luminescent functional materials, and particularly relates to a fluoro-lithium salt phosphorescent material and a preparation method thereof. Background Art

[0002] Due to its outstanding advantages such as long service life, fast response, no stroboscopic, energy conservation and environmental protection, white light LEDs have become the main choice for the backlight of the new generation of liquid crystal displays (LCDs). Currently, the mainstream commercial LED backlight obtains white light by the way of exciting red and green phosphors of Eu 2+ doped nitride with a blue LED chip. Since the emission spectrum of such white light LEDs is relatively wide, the color gamut of LCD devices is insufficient, making it difficult to meet the requirements of a wide color gamut backlight. In order to achieve vivid and realistic display colors, it is very important to reduce the line width of the red phosphor to increase the x value of the CIE chromaticity coordinates.

[0003] Mn 4+ Mn-doped all-inorganic fluoride phosphorescent materials are a type of red light materials that have gradually emerged in the past decade. In 2008, scientist Sadao Adachi from Gunma University in Japan synthesized a Mn 4+ -doped K2SiF6:Mn 4+ red light material in the HF solution etching experiment of a silicon wafer, which has an ultra-wideband absorption from the near ultraviolet region to the blue region and can emit bright narrow-band red light with extremely high color purity (J. Appl. Phys., 2008, 104, 023512). Subsequently, more and more scholars have devoted themselves to the research of Mn 4+ -doped all-inorganic fluoride phosphorescent materials. Currently, there are a large number of reports on Mn 4+ -doped all-inorganic fluoride red phosphors, which can be mainly divided into two major types: Mn 4+ equivalent-doped A2MF6:Mn 4+ (A: Li, Na, K, Rb, Cs, NH4; M: Si, Ge, Sn, Ti, Zr, Hf), and Mn 4+ heterovalent-doped A3NF6:Mn 4+ and A2XF7:Mn 4+ (A: Li, Na, K, Rb, Cs, NH4; N: Al, Ga, In, Sc; X: Nb, Ta). These all-inorganic red phosphors can be effectively excited by commercial blue LED chips, and have the advantages of high color purity, high luminous efficiency, simple preparation process, and no rare earths, etc., which have had a strong impact on the market of traditional Eu 2+ -doped nitride red phosphors. However, this type of Mn 4+Doped all-inorganic fluoride red phosphors still have problems of insufficient color coordinates and poor stability. Therefore, there is an urgent need to develop a new type of Mn 4+ -doped phosphorescent material with both a long red wavelength, high efficiency, and strong stability. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the purpose of the present invention is to overcome the shortcomings of the prior art and provide a fluorolithium phosphate material. This fluorolithium phosphate material can be applied to ultraviolet, near-ultraviolet or blue light-emitting diodes to fabricate high-quality white LED devices.

[0005] The purpose of the present invention also lies in providing a preparation method of the above-mentioned fluorolithium phosphate material, the preparation process is simple and feasible, the conditions are mild, and it can be mass-produced industrially.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] A fluorolithium phosphate material with a chemical composition of Ba 1-x Li 1-2x F3:xMn 4+ ; where x is the molar percentage coefficient of the doped ion Mn 4+ relative to the monovalent lithium ion, and 0 < x ≤ 5%.

[0008] Preferably, x is 0.01%, 0.05%, 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, etc.

[0009] Preferably, under the excitation of ultraviolet and near-ultraviolet light at 300 - 400 nm and blue light at 400 - 510 nm, the phosphorescent material can emit narrow-band red light with a main peak located at 600 - 660 nm, and the CIE color coordinate values are (0.7053 - 0.706, 0.2947 - 0.294), approaching the red light standard of REC.2020.

[0010] The preparation method of the above-mentioned fluorolithium phosphate material is prepared by a liquid-phase coprecipitation method or an ion exchange method.

[0011] Preferably, the liquid-phase coprecipitation method includes the following steps:

[0012] First, add fluoromanganate to a strong acid solution containing F - , stir for 5 - 10 minutes, and then add a compound containing Li + and a compound containing Ba 2+ to obtain a mixed solution, continue to stir for 5 - 360 minutes, and the obtained precipitate is collected, washed, and dried to obtain the fluorolithium phosphate material.

[0013] More preferably, the Ba2+ The compound is one or a combination of two or more of halides, acids, bases and salts containing Ba 2+ ;

[0014] More preferably, the compound containing Ba 2+ is one or a combination of two or more of barium nitrate and barium acetate.

[0015] Further preferably, the compound containing Li + is one or a combination of two or more of halides, acids, bases and salts containing Li + ;

[0016] More preferably, the compound containing Li + is one or a combination of two or more of lithium nitrate and lithium acetate.

[0017] Further preferably, the fluoromanganate is one or a combination of two or more of Li2MnF6, Na2MnF6, K2MnF6, Rb2MnF6, Cs2MnF6, (NH4)2MnF6, [(CH3)4N]2MnF6;

[0018] Further preferably, the strong acid solution containing F - is one or a combination of two or more of hydrofluoric acid solution, ammonium bifluoride solution and ammonium fluoride solution, and the pH of the strong acid solution containing F - ≤2.

[0019] Further preferably, in the mixed solution, the concentration of the compound containing Ba 2+ calculated as Ba 2+ is 0.1-1 moL / L;

[0020] Further preferably, in the compound containing Li + Li + , in the compound containing Ba 2+ Ba 2+ and in the strong acid solution containing F - F - the molar ratio is (1-1.5):1:(4-10), and in the fluoromanganate Mn 4+ and in the compound containing Ba 2+ Ba 2+ the molar ratio is greater than 0 and less than or equal to 0.05.

[0021] Preferably, the ion exchange method comprises the following steps:

[0022] (1) First, add the compound containing Li + and the compound containing Ba 2+ to the solution containing F -A mixed solution 1 is obtained in a strong acid solution, stirred for 5 - 360 minutes, and the obtained precipitate is collected, washed, and dried to obtain a BaLiF3 matrix precursor;

[0023] (2) Add a fluoromanganate to a strong acid solution containing F - , then add the BaLiF3 matrix precursor to obtain a mixed solution 2, continuously stir for 5 - 360 minutes, and the obtained precipitate is collected, washed, and dried to obtain the fluoro-lithium salt phosphorescent material.

[0024] Further preferably, the Ba-containing 2+ compound is one or a combination of two or more of the halides, acids, bases, and salts containing Ba 2+ ;

[0025] More preferably, the Ba-containing 2+ compound is one or a combination of two or more of barium nitrate and barium acetate.

[0026] Further preferably, the Li-containing + compound is one or a combination of two or more of the halides, acids, bases, and salts containing Li + ;

[0027] More preferably, the Li-containing + compound is one or a combination of two or more of lithium nitrate and lithium acetate.

[0028] Further preferably, the fluoromanganate is one or a combination of two or more of Li2MnF6, Na2MnF6, K2MnF6, Rb2MnF6, Cs2MnF6, (NH4)2MnF6, [(CH3)4N]2MnF6;

[0029] Further preferably, the strong acid solution containing F - is one or a combination of two or more of hydrofluoric acid solution, ammonium bifluoride solution, and ammonium fluoride solution, and the pH of the strong acid solution containing F - ≤2.

[0030] Further preferably, in the mixed solution 1 in step (1), the concentration of the Ba-containing 2+ compound in terms of Ba 2+ is 0.1 - 1 moL / L;

[0031] Further preferably, in the Li-containing + compound in step (1), Li + , in the Ba-containing 2+ compound, Ba 2+ , and in the strong acid solution containing F - F -The molar ratio is (1 - 1.5):1:(4 - 10);

[0032] Further preferably, in the mixed solution 2 described in step (2), the concentration of the BaLiF3 matrix precursor is 1 - 10 moL / L;

[0033] Further preferably, in the fluoromanganate described in step (2), Mn 4+ and Li in the BaLiF3 matrix precursor + The molar ratio is greater than 0 and less than or equal to 0.05.

[0034] Further preferably, the preparation method of the fluoromanganate includes the following steps:

[0035] First, dissolve the alkali metal fluoride or alkali metal hydrogen fluoride in the hydrofluoric acid solution, then add the permanganate or manganate, stir until completely dissolved, place the mixed solution in an ice bath state, and then gradually add hydrogen peroxide dropwise until the solution changes from purple to yellow and immediately stop adding, filter, and wash and dry the obtained precipitate to obtain the fluoromanganate.

[0036] More preferably, the alkali metal fluoride or alkali metal hydrogen fluoride is one or a combination of two or more of LiF, NaF, KF, RbF, CsF, KHF2, NaHF2; the permanganate or manganate is one or a combination of two or more of NaMnO4, KMnO4, BaMnO4, CaMnO4, Na2MnO4, K2MnO4.

[0037] Compared with the prior art, the advantages and positive effects of the present invention are:

[0038] (1) The fluoro-lithium salt phosphorescent material of the present invention has a long emission wavelength and is more excellent in the light-emitting characteristics of a wide color gamut than other Mn 4+ doped fluoride phosphorescent materials. In addition, it also has high chemical stability, short fluorescence lifetime and weather resistance, and can effectively improve the light color quality of the output white light when used in white LEDs, improve the performance and experience of products based on white LEDs, especially in high-end backlight display applications;

[0039] (2) The fluoro-lithium salt phosphorescent material of the present invention is in the form of a powder with uniform particle size, and is extremely easy to be mixed and dispersed with other fluorescent materials in epoxy resin or silica gel, and can be widely commercially applied to the fields of white LED lighting and backlight display;

[0040] (3) The preparation method of the present invention includes a liquid-phase co-precipitation method and an ion exchange method. The preparation process is simple, easy to operate, mild in conditions, and low in cost, and can be mass-produced industrially. Description of the Drawings

[0041] Figure 1 BaLiF3:Mn prepared in Example 1 4+ XRD powder diffraction pattern of the fluoro-lithium phosphate phosphor and the corresponding standard card pattern;

[0042] Figure 2 BaLiF3:Mn prepared in Example 1 4+ Room temperature excitation spectrum and emission spectrum of the fluoro-lithium phosphate phosphor;

[0043] Figure 3 BaLiF3:Mn prepared in Example 1 4+ Fluoro-lithium phosphate phosphor and commercial β-sialon:Eu 2+ Electroluminescence spectrum of the warm white LED device encapsulated with the green phosphor and the blue LED chip under 20 mA current excitation. Detailed implementation manners

[0044] The technical solutions of the present invention will be further described below in conjunction with specific embodiments and the accompanying drawings. However, the following embodiments are only for strengthening the description of the technical solutions of the present invention, and should not be construed as any limitation to the scope of the claimed invention. And the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts, any modifications, equivalent replacements, improvements, etc., shall be included in the protection scope of the present invention.

[0045] In the specific embodiments of the present invention, the preparation process of the fluoro-manganate specifically includes the following steps:

[0046] According to the chemical composition of X2MnF6 fluoro-manganate (X is an alkali metal cation), weigh alkali metal (X) fluoride or alkali metal (X) hydrogen fluoride and dissolve it in a hydrofluoric acid solution with a mass fraction of 49%. Add permanganate (X) or manganate (X). After all are dissolved, cool the mixed solution to 0 °C in an ice bath, and then gradually add 30 wt% hydrogen peroxide until the solution changes from purple to yellow, immediately stop adding, filter. The obtained precipitate is washed with acetone and dried at 80 °C for 2 hours to obtain the fluoro-manganate X2MnF6.

[0047] In the specific embodiments of the present invention, the fluoro-lithium phosphate phosphor is prepared by a liquid-phase co-precipitation method or an ion-exchange method. The liquid-phase co-precipitation method specifically includes the following steps:

[0048] (1) First, add the fluoro-manganate to a strong acid solution containing F - and stir for 5 - 10 minutes.

[0049] (2) Then add a solution containing Li +Compound and containing Ba 2+ The compound was continuously stirred for 5 - 360 minutes, and the obtained precipitate was collected, washed, and dried to obtain the fluoro-lithium salt phosphorescent material.

[0050] The ion exchange method specifically includes the following steps:

[0051] (1) First, the compound containing Li + Compound and containing Ba 2+ Compound were added to a strong acid solution containing F - , and stirred for 5 - 360 minutes. The obtained precipitate was collected, washed, and dried to obtain the BaLiF3 matrix precursor;

[0052] (2) The fluoro-manganate was added to a strong acid solution containing F - , and then the BaLiF3 matrix precursor was added, and continuously stirred for 5 - 360 minutes. The obtained precipitate was collected, washed, and dried to obtain the fluoro-lithium salt phosphorescent material.

[0053] Example 1

[0054] Using K2MnF6 as the manganese source, the BaLiF3:Mn 4+ fluoro-lithium salt phosphorescent material was prepared by the liquid-phase co-precipitation method, specifically including the following steps:

[0055] In a stirring environment, 1.2872 g of Ba(CH3COO)2 and 0.4137 g of LiNO3 were dissolved in 8 ml of deionized water. Then the obtained salt solution was added dropwise to 2 ml of an aqueous solution containing 0.8556 g of NH4HF2 and 0.01 g of K2MnF6, and stirred for 60 minutes to gradually form BaLiF3:Mn 4+ sample at room temperature. The product was collected after being washed with glacial acetic acid and ethanol multiple times, and then dried at 80 °C for 2 hours.

[0056] Attached Figure 1 Shown is the XRD powder diffraction pattern of the BaLiF3:Mn 4+ fluoro-lithium salt phosphorescent material. The diffraction peaks of the sample are consistent with the standard card pattern, and no diffraction peak signals of any impurity phases were observed, indicating that the synthesized BaLiF3:Mn 4+ fluoro-lithium salt phosphorescent material sample is a pure phase.

[0057] Attached Figure 2 Shown is the BaLiF3:Mn 4+Room-temperature excitation and emission spectra of fluorolithium phosphate phosphors. The samples have strong broad excitation bands in the ultraviolet and near-ultraviolet regions (320 nm - 420 nm) and the blue region (420 nm - 500 nm). Under excitation by blue light at ~470 nm, the samples emit narrow-band red light at 630 nm (the strongest emission peak), which consists of multiple sharp line peaks, with high color purity, approaching 100%.

[0058] Attached Figure 3 shows BaLiF3:Mn 4+ and commercial β-sialon:Eu 2+ The electroluminescence spectra of warm white LED devices encapsulated with green phosphors and blue LED chips under excitation by a 20 mA current. It can be seen from this figure that the blue emission peak at ~460 nm comes from the emission of the LED chip, and the emission peak at ~530 nm comes from the emission of the green phosphor β-sialon:Eu 2+ The emission of the fluorolithium phosphate phosphor BaLiF3:Mn 4+ is in the red region, and the strongest emission peak is at around ~630 nm. The white light emitted by this white LED is standard white light, with the characteristic of a wide color gamut.

[0059] Example 2

[0060] Using K2MnF6 as the manganese source, BaLiF3:Mn 4+ fluorolithium phosphate phosphors were prepared by an ion exchange method, specifically including the following steps:

[0061] (1) Preparation of the BaLiF3 matrix precursor: In a stirring environment, 1.2872 g of Ba(CH3COO)2 and 0.4137 g of LiNO3 were dissolved in 8 ml of deionized water. Then the obtained salt solution was added dropwise to a 2 ml aqueous solution containing 0.8556 g of NH4HF2, and stirred for 60 minutes to gradually form BaLiF3 samples at room temperature. The product was collected after being washed multiple times with glacial acetic acid and ethanol, and then dried at 80 °C for 2 hours.

[0062] (2) Preparation of BaLiF3:Mn 4+ fluorolithium phosphate phosphors: Weighed 0.1 g of K2MnF6 and dissolved it in 2 ml of hydrofluoric acid solution with a mass fraction of 49%. Then 2 g of the BaLiF3 matrix precursor was added, and stirring was continued for 30 minutes. The precipitate sample was collected by centrifugation, washed 3 times with acetone or ethanol, and dried at 60 °C for 4 hours to obtain BaLiF3:Mn 4+ fluorolithium phosphate phosphors.

[0063] BaLiF3:Mn prepared by the ion exchange method 4+The structure and luminescence properties of the fluorolithium phosphate phosphor are consistent with those of Example 1.

[0064] Example 3

[0065] Using Cs2MnF6 as the manganese source, BaLiF3:Mn was prepared by the liquid-phase co-precipitation method 4+ fluorolithium phosphate phosphor, specifically including the following steps:

[0066] In a stirring environment, 1.2872 g of Ba(CH3COO)2 and 0.4137 g of LiNO3 were dissolved in 8 ml of deionized water. Then the obtained salt solution was added dropwise to 2 ml of an aqueous solution containing 0.8556 g of NH4HF2 and 0.01 g of Cs2MnF6, and stirred for 60 minutes to gradually form BaLiF3:Mn 4+ sample at room temperature. The product was collected after being washed repeatedly with glacial acetic acid and ethanol, and then dried at 80 °C for 2 hours.

[0067] Using Cs2MnF6 as the manganese source, BaLiF3:Mn prepared by the co-precipitation method 4+ The structure and luminescence properties of the fluorolithium phosphate phosphor are consistent with those of Examples 1 and 2.

[0068] Example 4

[0069] Using Cs2MnF6 as the manganese source, BaLiF3:Mn was prepared by the ion-exchange method 4+ fluorolithium phosphate phosphor, specifically including the following steps:

[0070] (1) Preparation of BaLiF3 matrix precursor: In a stirring environment, 1.2872 g of Ba(CH3COO)2 and 0.4137 g of LiNO3 were dissolved in 8 ml of deionized water. Then the obtained salt solution was added dropwise to 2 ml of an aqueous solution containing 0.8556 g of NH4HF2, and stirred for 60 minutes to gradually form a BaLiF3 sample at room temperature. The product was collected after being washed repeatedly with glacial acetic acid and ethanol, and then dried at 80 °C for 2 hours.

[0071] (2) Preparation of BaLiF3:Mn 4+ fluorolithium phosphate phosphor: Weigh 0.1 g of Cs2MnF6 and dissolve it in 2 ml of a 49% by mass hydrofluoric acid solution. Then add 1 g of the BaLiF3 matrix precursor, and continuously stir for 30 minutes. Use a centrifuge to collect the precipitate sample, wash it 3 times with acetone or ethanol, and dry it at 60 °C for 4 hours to obtain BaLiF3:Mn 4+ fluorolithium phosphate phosphor.

[0072] BaLiF3:Mn prepared by an ion exchange method using Cs2MnF6 as the manganese source 4+ The structure, luminescence properties of the fluoro-lithium phosphors are consistent with those of Examples 1, 2, and 3.

[0073] BaLiF3:Mn synthesized according to the above liquid-phase method 4+ The fluoro-lithium phosphors have more excellent luminescence properties in a wide color gamut than other Mn 4+ doped fluoride phosphors. BaLiF3:Mn synthesized according to Examples 1-4 4+ The fluoro-lithium phosphors and some typical Mn 4+ The comparison of the optical properties such as emission wavelength and color coordinates between the doped fluoride phosphors is shown in Table 1 below.

[0074] Table 1 ZPL peak positions and color coordinate values of BaLiF3:Mn 4+ fluoro-lithium phosphors synthesized in Examples 1-4 and some typical fluoride phosphors.

[0075]

[0076] Note: The above data were measured under blue light (~470 nm) excitation. The color coordinates of the Rec.2020 red light standard issued by the International Telecommunication Union (ITU) are (0.708, 0.292).

[0077] The following details the synthesis methods of various Mn 4+ doped all-inorganic fluoride phosphors in the comparative examples above.

[0078] Comparative Example 1

[0079] The synthesis method of the phosphor K2SiF6:Mn 4+ is as follows:

[0080] Measure 0.3004 g of SiO2 and add it to 5 ml of a 49% by mass hydrofluoric acid solution, then add 0.12 g of K2MnF6, and then add 1.4525 g of potassium fluoride and stir for 30 - 360 minutes. Use a centrifuge to collect the precipitate sample, wash it 3 times with glacial acetic acid, acetone or ethanol, and dry it at 70 °C for 4 hours to obtain K2SiF6:Mn 4+ .

[0081] For the Mn 4+ doped all-inorganic fluoride phosphors in Comparative Examples 2-13, except for weighing the relevant raw materials according to their chemical formula compositions and stoichiometric ratios, the remaining preparation steps are the same as those in Comparative Example 1.

[0082] It should be understood that any modifications, substitutions, or changes made by those skilled in the art based on the true spirit of the present invention and on the basis of the specific embodiments of the present invention should be covered by the protection scope of the present invention.

Claims

1. A fluoro-lithium salt phosphorescent material, characterized in that, The chemical composition is Ba 1-x Li 1-2x F3:xMn 4+ ; where x is the doping ion Mn 4+ is the molar percentage coefficient relative to the monovalent lithium ions, and 0 < x ≤ 5%.

2. The fluoro-lithium phosphorescent material according to claim 1, characterized in that, Under the excitation of ultraviolet and near-ultraviolet light at 300 - 400 nm and blue light at 400 - 510 nm, the phosphorescent material can emit narrow-band red light with a main peak located at 600 - 660 nm, and the CIE color coordinate values are (0.7053 - 0.706, 0.2947 - 0.294).

3. The preparation method of the fluoro-lithium salt phosphorescent material according to claim 1 or 2, characterized in that, Prepared by the liquid-phase coprecipitation method or the ion-exchange method.

4. The preparation method of the fluoro-lithium salt phosphorescent material according to claim 3, characterized in that, The liquid-phase coprecipitation method includes the following steps: First, add fluoromanganate to a strong acid solution containing F - , stir for 5 - 10 minutes, then add a compound containing Li + and a compound containing Ba 2+ to obtain a mixed solution, continue to stir for 5 - 360 minutes, and the obtained precipitate is collected, washed, and dried to obtain the fluorolithium salt phosphorescent material.

5. The preparation method of the fluoro-lithium-phosphate phosphorescent material according to claim 4, characterized in that, The Ba-containing 2+ compound is one or a combination of two or more of a halide, an acid, a base, and a salt containing 2+ Ba; the Li-containing + compound is one or a combination of two or more of a halide, an acid, a base, and a salt containing + Li.

6. The preparation method of the fluoro-lithium salt phosphorescent material according to claim 4, characterized in that, The fluoromanganate is one or a combination of two or more of Li2MnF6, Na2MnF6, K2MnF6, Rb2MnF6, Cs2MnF6, (NH4)2MnF6, [(CH3)4N]2MnF6; The strong acid solution containing F - is one or a combination of two or more of hydrofluoric acid solution, ammonium bifluoride solution, and ammonium fluoride solution. The strong acid solution containing F - has a pH ≤ 2.

7. The preparation method of the fluoro-lithium salt phosphorescent material according to claim 4, characterized in that, In the mixed solution, it contains Ba 2+ The compound has a concentration of 0.1 - 1 moL / L in terms of Ba 2+ calculated; The Li-containing + Li in compounds + , containing 2+ Ba in the compound 2+ and containing F - F in strong acid solution - The molar ratio of Mn in the fluoromanganate is (1-1.5):1:(4-10); 4+ and containing Ba 2+ Ba in the compound 2+ The molar ratio is greater than 0 and less than or equal to 0.

05.

8. The preparation method of the fluoro-lithium salt phosphorescent material according to claim 3, characterized in that, The ion-exchange method includes the following steps: (1) First, add the Li + compound and the Ba 2+ compound to a strong acid solution containing F - to obtain a mixed solution 1, stir for 5 - 360 minutes, collect, wash, and dry the resulting precipitate to obtain a BaLiF3 matrix precursor; (2) Add fluoromanganate to a strong acid solution containing F - , then add the BaLiF3 matrix precursor to obtain a mixed solution 2. Continuously stir for 5 - 360 minutes. The obtained precipitate is collected, washed, and dried to obtain the fluorolithium salt phosphorescent material.

9. The preparation method of the fluoro-lithium salt phosphorescent material according to claim 8, characterized in that, The Ba-containing 2+ compound is one or a combination of two or more of the halides, acids, bases and salts containing 2+ Ba; the Li-containing + compound is one or a combination of two or more of the halides, acids, bases and salts containing + Li; The fluoromanganate is one or a combination of two or more of Li2MnF6, Na2MnF6, K2MnF6, Rb2MnF6, Cs2MnF6, (NH4)2MnF6, [(CH3)4N]2MnF6; The strong acid solution containing F - is one or a combination of two or more of hydrofluoric acid solution, ammonium bifluoride solution, and ammonium fluoride solution. The strong acid solution containing F - has a pH ≤ 2.

10. The preparation method of the fluoro-lithium salt phosphorescent material according to claim 8, wherein, In the mixed solution 1 described in step (1), the concentration of the Ba 2+ compound calculated as Ba 2+ is 0.1 - 1 moL / L; The Li in the compound described in step (1) + in the Li + compound, the Ba in the compound containing Ba 2+ and the F in the strong acid solution containing F 2+ have a molar ratio of (1 - 1.5):1:(4 - 10); - in the strong acid solution containing F - ​ In the mixed solution 2 in step (2), the concentration of the BaLiF3 matrix precursor is 1 - 10 moL / L; The Mn in the fluoromanganate described in step (2) 4+ and the Li in the BaLiF3 matrix precursor + have a molar ratio greater than 0 and less than or equal to 0.05.

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