CN114751431B - Preparation method of sodium salt for sodium battery - Google Patents
Preparation method of sodium salt for sodium battery Download PDFInfo
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- CN114751431B CN114751431B CN202210438732.3A CN202210438732A CN114751431B CN 114751431 B CN114751431 B CN 114751431B CN 202210438732 A CN202210438732 A CN 202210438732A CN 114751431 B CN114751431 B CN 114751431B
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- hexafluorophosphate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D13/00—Compounds of sodium or potassium not provided for elsewhere
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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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Abstract
The invention discloses a preparation method of sodium salt for a sodium battery, which comprises the following steps: uniformly mixing polyvinyl alcohol and sodium fluoride, adding deionized water, drying, and calcining to obtain porous sodium fluoride; introducing phosphorus pentafluoride gas into a mixture of porous sodium fluoride and hydrogen fluoride liquid, and reacting to prepare a sodium hexafluorophosphate solution; and crystallizing, filtering and drying the sodium hexafluorophosphate solution to obtain the sodium hexafluorophosphate. The porous sodium fluoride is used as a sodium source to prepare sodium hexafluorophosphate, so that the utilization rate of the precursor can be improved, and the yield is effectively increased; in addition, the yield of the product can be further improved by stirring crystallization.
Description
Technical Field
The invention belongs to the technical field of sodium batteries, and relates to a preparation method of a sodium salt for a sodium battery.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The sodium element has the advantages of rich resources and low cost, and the sodium ion battery is widely concerned. Sodium batteries have the following advantages: firstly, the sodium element is abundant in the earth, and the content of the sodium element in the earth crust is about 3%, and in comparison, the content of the sodium element in the earth crust is only 0.065%; secondly, the distribution of sodium is more uniform compared with that of lithium; thirdly, the sodium battery has higher safety and wider standard voltage range.
Sodium hexafluorophosphate is used as an important sodium salt of the sodium battery electrolyte, and has the advantages of high conductivity, stable solid electrolyte interface and the like. But the yield of the sodium hexafluorophosphate is low at present, and the actual requirement is difficult to meet.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a sodium salt for a sodium battery.
In order to realize the purpose, the invention is realized by the following technical scheme:
a preparation method of a sodium salt for a sodium battery comprises the following steps:
uniformly mixing polyvinyl alcohol, sodium fluoride and water to prepare mixed slurry, and then drying and calcining the slurry to obtain porous sodium fluoride;
introducing phosphorus pentafluoride gas into a mixture of porous sodium fluoride and hydrogen fluoride liquid, and reacting to prepare a sodium hexafluorophosphate solution;
and crystallizing, filtering and drying the sodium hexafluorophosphate solution to obtain the sodium hexafluorophosphate.
The beneficial effects achieved by one or more of the embodiments of the invention described above are as follows:
according to the invention, porous sodium fluoride is used as a sodium source to prepare sodium hexafluorophosphate, so that the utilization rate of the precursor can be improved, and the yield is effectively increased; in addition, the yield of the product can be further improved by stirring crystallization.
The invention has mild condition and simple process, and can effectively reduce the cost.
The sodium hexafluorophosphate obtained by using the anhydrous hydrogen fluoride as the solvent has high purity.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
A preparation method of a sodium salt for a sodium battery comprises the following steps:
uniformly mixing polyvinyl alcohol, sodium fluoride and water to prepare mixed slurry, and then drying and calcining the slurry to obtain porous sodium fluoride;
introducing phosphorus pentafluoride gas into a mixture of porous sodium fluoride and hydrogen fluoride liquid, and reacting to prepare a sodium hexafluorophosphate solution;
crystallizing the sodium hexafluorophosphate solution, filtering and drying to obtain the sodium hexafluorophosphate.
And drying the mixed slurry of the polyvinyl alcohol and the sodium fluoride, and calcining at high temperature to generate gas from the polyvinyl alcohol, thereby preparing the porous sodium fluoride.
In some embodiments, the mass ratio of polyvinyl alcohol to sodium fluoride is 1.
In some embodiments, the temperature of the calcination is 600 to 900 ℃ and the time of calcination is 0.5 to 5 hours.
In some embodiments, the mass ratio of the porous sodium fluoride to the hydrogen fluoride liquid is 1. The hydrogen fluoride liquid can act as a solvent on the one hand and can promote the reaction on the other hand. Sodium fluoride has certain solubility in hydrogen fluoride liquid, and the reactant is not dissolved if the sodium fluoride is too little; too much will reduce the yield.
In some embodiments, the phosphorus pentafluoride is reacted with the porous sodium fluoride at a temperature of 0 to 30 ℃ for a reaction time of 5 to 20 hours.
In some embodiments, the crystallization temperature is from-5 to 5 ℃ and the crystallization time is from 4 to 8 hours.
Preferably, the drying is vacuum drying, the temperature of the vacuum drying is 80-100 ℃, and the time of the vacuum drying is 12-24h.
The present invention will be further described with reference to the following examples.
Example 1
A preparation method of sodium hexafluorophosphate with high yield comprises the following steps:
synthesizing porous sodium fluoride: adding deionized water into 1g of sodium fluoride and 1g of polyvinyl alcohol, uniformly mixing, and then putting into an oven for drying. Calcining the dried product at 600 ℃ for 2h, and cooling to obtain the porous sodium fluoride.
Adding 1g of sodium fluoride and 10g of hydrogen fluoride into a reaction kettle, uniformly stirring, and controlling the temperature at 0 ℃.
Adding excessive phosphorus pentachloride into another reaction kettle, then slowly adding hydrogen fluoride, and introducing generated gas into the reaction kettle, wherein the temperature is controlled at 15 ℃.
And after the reaction is finished, cooling to 0 ℃, stirring and crystallizing for 5 hours to obtain a solid through a filter, and drying the solid in an air-evaporated drying oven to obtain the required sodium hexafluorophosphate product, wherein the yield of the sodium hexafluorophosphate is 94.5%, and the purity of the sodium hexafluorophosphate is 99.85%.
Example 2
A preparation method of high-yield sodium hexafluorophosphate comprises the following steps:
synthesizing porous sodium fluoride: adding deionized water into 5g of sodium fluoride and 1g of polyvinyl alcohol, uniformly mixing, and then putting into an oven for drying. Calcining the dried product at 800 ℃ for 1h, and cooling to obtain the porous sodium fluoride.
1g of sodium fluoride and 12g of hydrogen fluoride are added into a reaction kettle, the mixture is stirred uniformly, and the temperature is controlled at 2 ℃.
Adding excessive phosphorus pentachloride into another reaction kettle, then slowly adding hydrogen fluoride, and introducing the generated gas into the reaction kettle, wherein the temperature is controlled at 12 ℃.
And after the reaction is finished, cooling to 0 ℃, stirring and crystallizing for 5 hours to obtain a solid through a filter, and drying the solid in an air drying box to obtain the required sodium hexafluorophosphate product, wherein the yield of the sodium hexafluorophosphate is 94.9%, and the purity of the sodium hexafluorophosphate is 99.88%.
Example 3
A preparation method of high-yield sodium hexafluorophosphate comprises the following steps:
synthesizing porous sodium fluoride: adding deionized water into 4g of sodium fluoride and 1g of polyvinyl alcohol, uniformly mixing, and then putting into an oven for drying. Calcining the dried product at 850 ℃ for 0.5h, and cooling to obtain the porous sodium fluoride.
1g of sodium fluoride and 14g of hydrogen fluoride are added into a reaction kettle, the mixture is stirred uniformly, and the temperature is controlled at 5 ℃.
Adding excessive phosphorus pentachloride into another reaction kettle, then slowly adding hydrogen fluoride, and introducing the generated gas into the reaction kettle, wherein the temperature is controlled at 14 ℃.
And after the reaction is finished, cooling to 0 ℃, stirring and crystallizing for 5 hours to obtain a solid through a filter, and drying the solid in an air drying box to obtain the required sodium hexafluorophosphate product, wherein the yield of the sodium hexafluorophosphate is 95.2%, and the purity of the sodium hexafluorophosphate is 99.81%.
Example 4
A preparation method of sodium hexafluorophosphate with high yield comprises the following steps:
synthesizing porous sodium fluoride: and adding deionized water into 10g of sodium fluoride and 1g of polyvinyl alcohol, uniformly mixing, and then putting into an oven for drying. Calcining the dried product at 600 ℃ for 2h, and cooling to obtain the porous sodium fluoride.
Adding 1g of sodium fluoride and 10g of hydrogen fluoride into a reaction kettle, uniformly stirring, and controlling the temperature at 10 ℃.
Adding excessive phosphorus pentachloride into another reaction kettle, then slowly adding hydrogen fluoride, and introducing the generated gas into the reaction kettle, wherein the temperature is controlled at 15 ℃.
And after the reaction is finished, cooling to 0 ℃, stirring and crystallizing for 5 hours to obtain a solid through a filter, and drying the solid in an air drying box to obtain the required sodium hexafluorophosphate product, wherein the yield of the sodium hexafluorophosphate is 94.4%, and the purity of the sodium hexafluorophosphate is 99.91%.
Example 6
A preparation method of high-yield sodium hexafluorophosphate comprises the following steps:
synthesizing porous sodium fluoride: taking 12g of sodium fluoride and 1g of polyvinyl alcohol, adding deionized water, uniformly mixing, and then putting into an oven for drying. Calcining the dried product at 700 ℃ for 1.8h, and cooling to obtain the porous sodium fluoride.
Adding 1g of sodium fluoride and 18g of hydrogen fluoride into a reaction kettle, uniformly stirring, and controlling the temperature at 8 ℃.
Adding excessive phosphorus pentachloride into another reaction kettle, then slowly adding hydrogen fluoride, and introducing the generated gas into the reaction kettle, wherein the temperature is controlled at 10 ℃.
And after the reaction is finished, cooling to 0 ℃, stirring and crystallizing for 5 hours to obtain a solid through a filter, and drying the solid in an air-evaporated drying oven to obtain the required sodium hexafluorophosphate product, wherein the yield of the sodium hexafluorophosphate is 96.1 percent, and the purity of the sodium hexafluorophosphate is 99.84 percent.
Comparative example 1
The difference from example 1 is that: the porous sodium fluoride in example 1 was replaced with commercially available sodium fluoride, and the procedure was otherwise the same as in example 1.
The yield of sodium hexafluorophosphate was 84.3% and the purity was 99.42%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of sodium salt for a sodium battery is characterized by comprising the following steps: the method comprises the following steps:
uniformly mixing polyvinyl alcohol, sodium fluoride and water to prepare mixed slurry, and then drying and calcining the slurry to obtain porous sodium fluoride;
introducing phosphorus pentafluoride gas into a mixture of porous sodium fluoride and hydrogen fluoride liquid, and reacting to prepare a sodium hexafluorophosphate solution;
crystallizing, filtering and drying the sodium hexafluorophosphate solution to obtain sodium hexafluorophosphate;
the mass ratio of polyvinyl alcohol to sodium fluoride is 1-15; the calcining temperature is 600-900 ℃, and the calcining time is 0.5-5h.
2. The method for producing a sodium salt for a sodium battery according to claim 1, characterized in that: the mass ratio of the porous sodium fluoride to the hydrogen fluoride liquid is 1.
3. The method for producing a sodium salt for a sodium battery according to claim 1, characterized in that: the reaction temperature of the phosphorus pentafluoride and the porous sodium fluoride is 0-30 ℃, and the reaction time is 5-20h.
4. The method for producing a sodium salt for a sodium battery according to claim 3, characterized in that: the reaction temperature of the phosphorus pentafluoride and the porous sodium fluoride is 10-20 ℃, and the reaction time is 5-20h.
5. The method for producing a sodium salt for a sodium battery according to claim 1, characterized in that: the crystallization temperature is-5 to 5 ℃, and the crystallization time is 4 to 8 hours.
6. The method for producing a sodium salt for a sodium battery according to claim 5, characterized in that: the crystallization temperature is 0 ℃, and the crystallization time is 5h.
7. The method for producing a sodium salt for a sodium battery according to claim 1, characterized in that: the drying is vacuum drying.
8. The method for producing a sodium salt for a sodium battery according to claim 7, characterized in that: the vacuum drying temperature is 80-100 deg.C, and the vacuum drying time is 12-24h.
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| CN117361584A (en) * | 2023-09-26 | 2024-01-09 | 山东立中新能源材料有限公司 | Method for preparing sodium hexafluorophosphate for sodium battery by utilizing sodium hydrogen fluoride |
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