CN108963249B - Fluoride and preparation method and application thereof - Google Patents

Fluoride and preparation method and application thereof Download PDF

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CN108963249B
CN108963249B CN201810943226.3A CN201810943226A CN108963249B CN 108963249 B CN108963249 B CN 108963249B CN 201810943226 A CN201810943226 A CN 201810943226A CN 108963249 B CN108963249 B CN 108963249B
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fluoride
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glycerol
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reaction kettle
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CN108963249A (en
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袁中直
林锦芳
朱立才
何仲
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South China Normal University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/582—Halogenides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a fluoride and a preparation method and application thereof. The preparation method comprises the following steps: 1) adding metal salt and glycerol into a solvent, and carrying out solvothermal reaction to obtain a glycerol metal complex; 2) adding a glycerol metal complex and villiaumite into a solvent, and carrying out solvothermal reaction to obtain fluoride; wherein the metal salt is soluble metal salt, and the fluorine salt is soluble fluorine salt. The preparation method is simple and reliable, the reaction condition is mild, and hydrogen fluoride is not used, so that the preparation method is more environment-friendly and safer; meanwhile, the fluoride prepared by the invention has a special double-sphere hollow structure, has a larger specific surface area, is beneficial to the storage of electrolyte and the transmission of lithium ions when being used as an electrode active material, shows better discharge performance, has more catalytic reaction active points when being used as a catalyst in organic synthesis, has a better catalytic effect, and has controllable morphology.

Description

Fluoride and preparation method and application thereof
Technical Field
The invention relates to the field of material preparation, in particular to fluoride and a preparation method and application thereof.
Background
In recent years, lithium ion batteries are widely used in smart grids, portable electronic devices, medical fields, microelectronic manufacturing, electric vehicles, and the like. However, the lithium ion batteries in the current market are mainly embedded type reaction mode batteries, and the number of the lithium ions which are embedded or extracted is not more than 1, so that the specific capacity of the lithium ion batteries is low and is only 130-160 mAh/g. Fluoride as a conversion type positive electrode material can fully utilize all oxidation states of metals, can realize multi-electron conversion in an electrochemical reaction process, shows high specific capacity, becomes one of important research points of the positive electrode material, and is widely applied to the field of synthesis of organic compounds or organic fluorine compounds as an important catalyst and a carrier.
Chinese patent CN105336946A discloses a method for preparing ferric fluoride anode material, which is simple, but the fluorine source is hydrogen fluoride, both hydrogen fluoride and its aqueous solution are toxic, which is easy to make bones and teeth malformed, and hydrofluoric acid can be absorbed by mucous membrane, respiratory tract and gastrointestinal tract through skin, which is not good for human health; chinese patent CN1145275 discloses an AlF3A process for the preparation ofFluorination of SiO with HF by gas phase fluorination2-Al2O3Obtaining porous fluoride; chinese patent CN101863502A discloses a specific surface area of 114m2About/g β -AlF3The preparation method of (1), mixing gamma-Al2O3Soaking in carbon source water solution, drying, carbonizing, gas phase fluorinating to obtain carbon-containing fluoride, decarbonizing, acid treating, and calcining to obtain β -AlF with high specific surface3Although the specific surface area of the fluoride prepared by the method is higher, the preparation process is more complex and is not suitable for industrial production; european patent EP1440939A1 discloses an HS-AlF3The preparation method adopts a sol-gel method and adopts aluminum isopropoxide and CCl2F2And HS-AlF prepared by using HF gas as raw material3Although the specific surface area of the fluoride prepared by the method is high, HF gas is adopted as a fluorine source in the preparation process, the operation is difficult, the process is complex, the price of aluminum isopropoxide is high, and the prepared fluoride is in an amorphous structure.
Therefore, the preparation method and the process flow of the fluoride are complex, the raw materials are expensive or have high toxicity, most of the prepared fluoride is irregular blocky fluoride or solid spherical fluoride, the specific surface area of the fluoride is not high, and the like.
Therefore, the preparation method of the fluoride, which is green and environment-friendly, simple in preparation method and large in specific surface area, has important practical significance for further application of the fluoride.
Disclosure of Invention
The invention aims to provide a fluoride and a preparation method and application thereof.
The invention provides a simple, efficient, environment-friendly and cheap preparation method aiming at the problems of complex preparation method, expensive raw materials, no environmental protection and the like of the fluoride in the prior art, and the fluoride prepared by the preparation method has a special appearance.
Specifically, the technical scheme adopted by the invention is as follows:
one of the purposes of the invention is to provide a preparation method of fluoride, which comprises the following steps:
1) adding metal salt and glycerol into a solvent, and carrying out solvothermal reaction to obtain a glycerol metal complex;
2) adding a glycerol metal complex and villiaumite into a solvent, and carrying out solvothermal reaction to obtain fluoride;
wherein the metal salt is soluble metal salt, and the fluorine salt is soluble fluorine salt.
Preferably, the mass-to-volume ratio of the metal salt to the glycerol in the step 1) is 0.05-0.5 g/mL.
More preferably, the mass-to-volume ratio of the metal salt to the glycerol in the step 1) is 0.05-0.3 g/mL.
Preferably, the volume ratio of glycerol to solvent in step 1) is 1: (1-10).
More preferably, the volume ratio of glycerol to solvent in step 1) is 1: (3-7).
Preferably, the temperature of the solvothermal reaction in the step 1) is 100-200 ℃.
More preferably, the temperature of the solvothermal reaction in the step 1) is 120-180 ℃.
Preferably, the solvothermal reaction time in the step 1) is 1-12 h; more preferably, the solvothermal reaction time in the step 1) is 3-9 h.
Preferably, the molar ratio of the metal ion in the glycerol metal complex to the fluoride ion in the fluoride salt in step 2) is 1: (3-8).
Preferably, the temperature of the solvothermal reaction in the step 2) is 80-200 ℃.
More preferably, the temperature of the solvothermal reaction in the step 2) is 100-180 ℃.
Preferably, the solvothermal reaction time in the step 2) is 1-15 h; more preferably, the solvothermal reaction time in the step 2) is 3-10 h.
Preferably, the solvent in step 1) and step 2) is independently selected from at least one of methanol, ethanol, ethylene glycol, propanol, isopropanol, 1, 2-propanediol, 1, 3-propanediol, glycerol, n-butanol, 1, 2-butanediol, 1, 3-butanediol, 1, 4-butanediol, and n-pentanol.
Preferably, the metal salt is at least one selected from the group consisting of aluminum salt, iron salt, cobalt salt, nickel salt, copper salt, manganese salt and zinc salt.
Preferably, the fluorine salt is at least one selected from the group consisting of ammonium fluoride, lithium fluoride, ammonium bifluoride, sodium fluoride and potassium fluoride.
More preferably, the fluorine salt is at least one selected from the group consisting of ammonium fluoride and ammonium bifluoride.
Preferably, the solvent thermal reaction of step 1) and step 2) is finished, and the method further comprises the steps of filtering, washing, drying and the like.
Preferably, the fluoride obtained in step 2) has a double-sphere hollow structure.
The invention also aims to provide application of the fluoride prepared by the method.
The fluoride prepared by the method is used as an electrode active material in lithium batteries and capacitors or used as a catalyst and a carrier in organic synthesis.
The invention also provides a fluoride with a double-sphere hollow structure.
The specific surface area of the fluoride with the double-sphere hollow structure is 60-100 m2/g。
Preferably, the fluoride with the double-sphere hollow structure is prepared by the preparation method.
The invention has the beneficial effects that:
1. the preparation method is simple and reliable, the reaction condition is mild, and hydrogen fluoride is not used, so that the method is more environment-friendly and safer.
2. The fluoride prepared by the invention has a special double-sphere hollow structure, has a larger specific surface area, is beneficial to the storage of electrolyte and the transmission of lithium ions when being used as an electrode active material, shows better discharge performance, has more catalytic reaction active points when being used as a catalyst in organic synthesis, has a better catalytic effect, and has controllable morphology.
Drawings
FIG. 1 is an SEM image of ferric fluoride prepared in example 1;
FIG. 2 is a high magnification SEM image of ferric fluoride prepared in example 1;
figure 3 is an XRD pattern of iron fluoride prepared in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples. It will also be understood that the following examples are included merely for purposes of further illustrating the invention and are not to be construed as limiting the scope of the invention, as the invention extends to insubstantial modifications and adaptations of the invention following in the light of the principles set forth herein. The specific process parameters and the like of the following examples are also only one example of suitable ranges, and the skilled person can make a selection within the suitable ranges through the description herein, and are not limited to the specific data of the following examples.
Example 1
A preparation method of fluoride comprises the following steps:
1) taking 1.125g of ferric nitrate nonahydrate, 8mL of glycerol and 40mL of isopropanol, stirring and mixing uniformly, transferring the mixture into a reaction kettle, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying the lining to obtain the glyceryl iron complex;
2) and (3) putting 40mg of ferric glycerol complex, 10mL of isopropanol and 50mg of ammonium fluoride into a reaction kettle, stirring and mixing uniformly, sealing the reaction kettle, putting the reaction kettle into a blast oven, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying to obtain the ferric fluoride.
The morphology of the ferric fluoride prepared in example 1 is shown in fig. 1 and fig. 2, and it can be seen from fig. 1 that: the ferric fluoride prepared in this embodiment has a spherical structure, and the diameter of the ferric fluoride is about 2 to 4 μm, as can be further observed from the enlarged view of fig. 2, the ferric fluoride prepared in this embodiment has a double-sphere hollow structure, that is: still include a pellet in the outer layer big ball, and be hollow between ball and the ball, particle structure is regular simultaneously, and specific surface is big, and when it as electrode active material, be favorable to the storage of electrolyte, increase electrolyte and electrode active material's area of contact, improve electrochemistry interfacial reaction rate, demonstrate more excellent electrochemical performance, when it as the catalyst in the organic synthesis, possess more catalytic reaction active points, have better catalytic effect.
The XRD of the iron fluoride prepared in example 1 is shown in fig. 3, and it can be seen from fig. 3 that: peaks appeared around 15 °, 23 °, 27 ° and 49 °, which are FeF3·0.33H2The characteristic diffraction peak of O indicates that the ferric fluoride is successfully prepared by the method, and the prepared ferric fluoride is FeF3·0.33H2O。
Example 2
A preparation method of fluoride comprises the following steps:
1) taking 1.125g of ferric nitrate nonahydrate, 8mL of glycerol and 40mL of ethanol, stirring and mixing uniformly, transferring the mixture into a reaction kettle, carrying out solvothermal reaction for 10 hours at 120 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying the lining to obtain the ferric glyceryl complex;
2) and (3) putting 40mg of ferric glycerol complex, 10mL of isopropanol and 50mg of ammonium fluoride into a reaction kettle, stirring and mixing uniformly, sealing the reaction kettle, putting the reaction kettle into a blast oven, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying to obtain the ferric fluoride.
Example 3
A preparation method of fluoride comprises the following steps:
1) taking 1.125g of ferric nitrate nonahydrate, 8mL of glycerol and 40mL of isopropanol, stirring and mixing uniformly, transferring the mixture into a reaction kettle, carrying out solvothermal reaction for 2h at 200 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying the lining to obtain the glyceryl iron complex;
2) and (3) putting 40mg of ferric glycerol complex, 10mL of isopropanol and 50mg of ammonium fluoride into a reaction kettle, stirring and mixing uniformly, sealing the reaction kettle, putting the reaction kettle into a blast oven, carrying out solvothermal reaction for 10 hours at the temperature of 120 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying to obtain the ferric fluoride.
Example 4
A preparation method of fluoride comprises the following steps:
1) taking 1.125g of ferric nitrate nonahydrate, 5mL of glycerol and 40mL of isopropanol, stirring and mixing uniformly, transferring the mixture into a reaction kettle, carrying out solvothermal reaction for 10 hours at 120 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying the lining to obtain the glyceryl iron complex;
2) and (3) putting 40mg of ferric glycerol complex, 10mL of isopropanol and 50mg of ammonium fluoride into a reaction kettle, stirring and mixing uniformly, sealing the reaction kettle, putting the reaction kettle into a blast oven, carrying out solvothermal reaction for 12h at the temperature of 100 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying to obtain the ferric fluoride.
Example 5
A preparation method of fluoride comprises the following steps:
1) taking 1.125g of ferric nitrate nonahydrate, 8mL of glycerol and 40mL of 1, 2-propylene glycol, stirring and mixing uniformly, transferring the mixture into a reaction kettle, carrying out solvothermal reaction for 12h at 100 ℃, taking out an inner liner after the reaction kettle is cooled to room temperature, and filtering, washing and drying the inner liner to obtain the glycerol iron complex;
2) and (3) putting 50mg of ferric glyceroxide complex, 10mL of isopropanol and 62.7mg of ammonium fluoride into a reaction kettle, stirring and mixing uniformly, sealing the reaction kettle, putting the reaction kettle into a blast oven, carrying out solvothermal reaction for 10 hours at the temperature of 120 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying to obtain the ferric fluoride.
Example 6
A preparation method of fluoride comprises the following steps:
1) taking 1.875g of ferric nitrate nonahydrate, 8mL of glycerol and 40mL of isopropanol, stirring and mixing uniformly, transferring the mixture into a reaction kettle, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying the lining to obtain the glyceryl iron complex;
2) and (3) putting 50mg of ferric glycerol complex, 10mL of ethanol and 62.7mg of ammonium fluoride into a reaction kettle, stirring and mixing uniformly, sealing the reaction kettle, putting the reaction kettle into a blast oven, carrying out solvothermal reaction for 10 hours at the temperature of 120 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying to obtain the ferric fluoride.
Example 7
A preparation method of fluoride comprises the following steps:
1) taking 1.125g of ferric nitrate nonahydrate, 8mL of glycerol and 40mL of isopropanol, stirring and mixing uniformly, transferring the mixture into a reaction kettle, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying the lining to obtain the glyceryl iron complex;
2) and (3) putting 40mg of ferric glyceroxide complex, 10mL of isopropanol and 50mg of ammonium bifluoride into a reaction kettle, stirring and mixing uniformly, sealing the reaction kettle, putting the reaction kettle into a blast oven, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying to obtain the ferric fluoride.
Example 8
A preparation method of fluoride comprises the following steps:
1) taking 1.125g of aluminum nitrate nonahydrate, 8mL of glycerol and 40mL of isopropanol, stirring and mixing uniformly, transferring the mixture into a reaction kettle, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying the lining to obtain a glycerol aluminum complex;
2) and (3) putting 40mg of glycerol aluminum complex, 10mL of isopropanol and 50mg of ammonium fluoride into a reaction kettle, stirring and mixing uniformly, sealing the reaction kettle, putting the reaction kettle into a blast oven, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying to obtain the aluminum fluoride.
Example 9
A preparation method of fluoride comprises the following steps:
1) taking 1.125g of nickel nitrate hexahydrate, 8mL of glycerol and 40mL of isopropanol, stirring and mixing uniformly, transferring the mixture into a reaction kettle, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying the lining to obtain a nickel glycerol complex;
2) and (3) putting 40mg of nickel glycerol complex, 10mL of isopropanol and 50mg of ammonium fluoride into a reaction kettle, stirring and mixing uniformly, sealing the reaction kettle, putting the reaction kettle into a blast oven, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying to obtain the nickel fluoride.
Example 10
A preparation method of fluoride comprises the following steps:
1) taking 1.125g of cobalt nitrate hexahydrate, 8mL of glycerol and 40mL of isopropanol, stirring and mixing uniformly, transferring the mixture into a reaction kettle, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out an inner liner after the reaction kettle is cooled to room temperature, and filtering, washing and drying the inner liner to obtain a cobalt glycerol complex;
2) and (3) putting 40mg of the cobalt glycerol complex, 10mL of isopropanol and 50mg of ammonium fluoride into a reaction kettle, stirring and mixing uniformly, sealing the reaction kettle, putting the reaction kettle into a blast oven, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying to obtain the cobalt fluoride.
Example 11
A preparation method of fluoride comprises the following steps:
1) taking 1.125g of copper nitrate, 8mL of glycerol and 40mL of isopropanol, stirring and mixing uniformly, transferring the mixture into a reaction kettle, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying the lining to obtain a copper glycerol complex;
2) and (3) putting 40mg of copper glycerol complex, 10mL of isopropanol and 50mg of ammonium fluoride into a reaction kettle, stirring and mixing uniformly, sealing the reaction kettle, putting the reaction kettle into a blast oven, carrying out solvothermal reaction for 6 hours at 160 ℃, taking out the lining after the reaction kettle is cooled to room temperature, and filtering, washing and drying to obtain the copper fluoride.
The fluoride prepared in the examples 2 to 11 has a similar morphology structure as that of the fluoride prepared in the example 1.

Claims (8)

1. A preparation method of fluoride is characterized in that: the method comprises the following steps:
1) adding metal salt and glycerol into a solvent, and carrying out solvothermal reaction to obtain a glycerol metal complex;
2) adding a glycerol metal complex and villiaumite into a solvent, and carrying out solvothermal reaction to obtain fluoride;
wherein the metal salt is soluble metal salt, and the villiaumite is soluble villiaumite; the volume ratio of the glycerol to the solvent in the step 1) is 1: 3-7; the temperature of the solvothermal reaction in the step 1) is 100-200 ℃; the temperature of the solvothermal reaction in the step 2) is 100-200 ℃; the fluoride obtained in the step 2) has a double-sphere hollow structure.
2. The method of claim 1, wherein: the mass-volume ratio of the metal salt to the glycerol in the step 1) is 0.05-0.5 g/mL.
3. The method of claim 1, wherein: the molar ratio of the metal ions in the glycerol metal complex to the fluorine ions in the fluorine salt in the step 2) is 1: 3 to 8.
4. The method of claim 1, wherein: the solvent in the step 1) and the step 2) is at least one selected from methanol, ethanol, ethylene glycol, propanol, isopropanol, 1, 2-propylene glycol, 1, 3-propylene glycol, glycerol, n-butanol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 4-butylene glycol and n-amyl alcohol.
5. The method of claim 1, wherein: the metal salt is at least one of aluminum salt, ferric salt, cobalt salt, nickel salt, copper salt, manganese salt and zinc salt.
6. The method of claim 1, wherein: the fluorine salt is selected from at least one of ammonium fluoride, lithium fluoride, ammonium bifluoride, sodium fluoride and potassium fluoride.
7. The use of the fluoride prepared by the preparation method according to any one of claims 1 to 6 as an electrode active material in lithium batteries and capacitors or as a catalyst and a carrier in organic synthesis.
8. A fluoride with a double-sphere hollow structure is characterized in that: the fluoride is prepared by the preparation method of any one of claims 1 to 6, and the specific surface area of the fluoride is 60 to 100m2/g。
CN201810943226.3A 2018-08-17 2018-08-17 Fluoride and preparation method and application thereof Active CN108963249B (en)

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CN115706215B (en) * 2021-08-16 2024-04-12 北京钠谛科技有限公司 Novel high-specific-capacity high-magnification fluorine-oxygen-containing lithium battery negative electrode material and preparation method thereof

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CN105314685A (en) * 2014-07-31 2016-02-10 中国科学院上海硅酸盐研究所 High-performance nano manganous fluoride cathode material and preparation method therefor
CN106684348A (en) * 2016-12-19 2017-05-17 西安近代化学研究所 Nano iron fluoride-based composite material, and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105314685A (en) * 2014-07-31 2016-02-10 中国科学院上海硅酸盐研究所 High-performance nano manganous fluoride cathode material and preparation method therefor
CN106684348A (en) * 2016-12-19 2017-05-17 西安近代化学研究所 Nano iron fluoride-based composite material, and preparation method thereof

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