CN116924437B - Sodium salt preparation method and sodium ion battery - Google Patents
Sodium salt preparation method and sodium ion battery Download PDFInfo
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- CN116924437B CN116924437B CN202311203558.5A CN202311203558A CN116924437B CN 116924437 B CN116924437 B CN 116924437B CN 202311203558 A CN202311203558 A CN 202311203558A CN 116924437 B CN116924437 B CN 116924437B
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- 159000000000 sodium salts Chemical class 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 14
- -1 sodium alkoxide Chemical class 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 45
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 45
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 40
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 40
- 239000011734 sodium Substances 0.000 claims abstract description 40
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 150000001450 anions Chemical class 0.000 claims abstract description 9
- 238000000746 purification Methods 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 12
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 claims description 3
- 229940074371 monofluorophosphate Drugs 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 abstract description 9
- 239000011737 fluorine Substances 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229940063013 borate ion Drugs 0.000 description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 2
- 239000004312 hexamethylene tetramine Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- 229940005638 monofluorophosphate ion Drugs 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XXYVTWLMBUGXOK-UHFFFAOYSA-N [Na].FS(=N)F Chemical compound [Na].FS(=N)F XXYVTWLMBUGXOK-UHFFFAOYSA-N 0.000 description 1
- VHSLGFZDYCMVHY-UHFFFAOYSA-N boric acid;oxalyl difluoride Chemical compound OB(O)O.FC(=O)C(F)=O VHSLGFZDYCMVHY-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- ISXSFOPKZQZDAO-UHFFFAOYSA-N formaldehyde;sodium Chemical compound [Na].O=C ISXSFOPKZQZDAO-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- 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
In order to solve the problems of complex operation and insufficient product purity in the existing preparation of fluorine-containing sodium salt from fluorine-containing ammonium salt, the invention provides a sodium salt preparation method and a sodium ion battery, wherein the sodium salt preparation method comprises the following operation steps: mixing reaction: reacting sodium alkoxide, an ammonium salt and paraformaldehyde to obtain a mixture containing sodium salt, wherein the sodium salt and the ammonium salt have the same anions; purifying: purification from the mixture gave sodium salt. Meanwhile, the invention also discloses a sodium ion battery. The preparation method provided by the invention effectively improves the preparation efficiency and the purity of the sodium salt obtained by preparation, reduces the subsequent purification difficulty, is beneficial to obtaining the high-purity sodium salt of the battery grade and improves the electrochemical performance of the sodium ion battery.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery materials, and particularly relates to a sodium salt preparation method and a sodium ion battery.
Background
The sodium ion battery has the outstanding advantages of abundant resources, low price, wide distribution and the like, and becomes an optional system of the energy storage system. As an important constituent of a battery, factors such as stability, safety, etc. of an electrolyte are important factors for achieving the safety performance of the battery.
At present, sodium salt is usually added into electrolyte in a sodium ion battery as electrolyte salt, and common sodium salts comprise sodium hexafluorophosphate, sodium difluorophosphate, sodium difluorosulfimide and other fluorine-containing sodium salts.
Compared with fluorine-containing sodium salt, the fluorine-containing ammonium salt is more stable in the state of the solution, the preparation difficulty is lower, and the impurity removal and purification are easier to obtain a high-purity product. Thus, there is a preparation route for preparing a fluorine-containing sodium salt in high purity by fluorine-containing ammonium salt. For example, in the prior art, CN108217622a is reacted with sodium hydroxide, sodium methoxide or sodium ethoxide to obtain sodium hexafluorophosphate, but in this reaction, sodium methoxide or sodium ethoxide is prone to side reactions with ammonium hexafluorophosphate, especially reactions with hexafluorophosphate groups lead to more byproducts in the reaction process, so that the obtained sodium hexafluorophosphate has more byproducts, needs to be purified for multiple times, and has the defects of complex operation and insufficient purity of the product.
Disclosure of Invention
Aiming at the problems of complex operation and insufficient product purity in the existing preparation of fluorine-containing sodium salt from fluorine-containing ammonium salt, the invention provides a sodium salt preparation method and a sodium ion battery.
The technical scheme adopted by the invention for solving the technical problems is as follows:
in one aspect, the invention provides a method for preparing sodium salt, comprising the following steps:
mixing reaction: reacting sodium alkoxide, ammonium salt and paraformaldehyde to obtain a mixture containing sodium salt, wherein the sodium salt and the ammonium salt have the same anions, and the sodium alkoxide comprises one or more of sodium methoxide, sodium ethoxide and sodium propoxide; the paraformaldehyde is selected from short-line chain polymerization state paraformaldehyde with the polymerization degree of 8-100;
purifying: purification from the mixture gave sodium salt.
Optionally, the anion of the ammonium salt is selected from one or more of hexafluorophosphate ion, difluorophosphate ion, monofluorophosphate ion, difluorooxalate borate ion, dioxaborate ion and difluorosulfonimide ion.
Optionally, the molar ratio of sodium alkoxide to ammonium salt to paraformaldehyde is (3-10): (2-4): (1-3).
Optionally, in the "mixed reaction" operation, the reaction temperature is 0-30 ℃.
Optionally, in the operation of "mixing reaction", sodium alkoxide is pre-dissolved in a first solvent to prepare sodium alkoxide solution, and the sodium alkoxide solution is adopted to participate in the system reaction.
Optionally, the first solvent comprises one or more of methanol, ethanol, acetonitrile, chloroform, dichloromethane, ethylene glycol dimethyl ether, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, and ethyl acetate.
Optionally, in the operation of "mixing reaction", the paraformaldehyde is dissolved in the second solvent to prepare a paraformaldehyde solution, and the paraformaldehyde solution is adopted to participate in the system reaction, or the paraformaldehyde is directly and solid put into the reaction system.
Optionally, the second solvent includes one or more of methanol, ethanol, acetonitrile, chloroform, dichloromethane, ethylene glycol dimethyl ether, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, and ethyl acetate.
Optionally, in the "mixed reaction" operation, the material adding sequence is as follows: the paraformaldehyde and the ammonium salt are not mixed in the absence of sodium alkoxide.
In another aspect, the invention provides a sodium ion battery comprising a positive electrode, a negative electrode and a sodium salt, the sodium salt being prepared by the preparation method as described above.
According to the preparation method provided by the invention, the ammonium salt and sodium alkoxide are adopted to react to prepare the sodium salt, in order to avoid unnecessary side reactions between the ammonium salt and the sodium alkoxide, paraformaldehyde is added into the system, and the inventor finds that the reaction between the ammonium salt and the sodium alkoxide can be effectively promoted by adding the paraformaldehyde, and meanwhile, the side reactions generated by anions of the ammonium salt are inhibited, so that a mixed reaction product comprising the sodium salt, the hexamethylenetetramine, the alcohol and the sodium hydroxide is obtained.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The embodiment of the invention provides a preparation method of sodium salt, which comprises the following operation steps:
mixing reaction: reacting sodium alkoxide, ammonium salt and paraformaldehyde to obtain a mixture containing sodium salt, wherein the sodium salt and the ammonium salt have the same anions, and the sodium alkoxide comprises one or more of sodium methoxide, sodium ethoxide and sodium propoxide; the paraformaldehyde is selected from short-chain polymerization state paraformaldehyde with the polymerization degree of 8-100.
Purifying: purification from the mixture gave sodium salt.
In the preparation method, the ammonium salt and sodium alkoxide are adopted to react to prepare the sodium salt, in order to avoid unnecessary side reaction between the ammonium salt and sodium alkoxide, paraformaldehyde is added into the system, and the inventor finds that the reaction between ammonium and sodium formaldehyde can be effectively promoted by adding the paraformaldehyde, and meanwhile, the side reaction generated by anions of the ammonium salt is restrained, so that a mixed reaction product comprising the sodium salt, hexamethylenetetramine, methanol and sodium hydroxide is obtained.
In some embodiments, the anion of the ammonium salt is selected from one or more of hexafluorophosphate ion, difluorophosphate ion, monofluorophosphate ion, difluorooxalato borate ion, dioxaoxalato borate ion, and difluorosulfonimide ion.
In some embodiments, the molar ratio of sodium alkoxide, ammonium salt, and paraformaldehyde is (3-10): (2-4): (1-3).
In some embodiments, the "mixing reaction" operation is performed at a reaction temperature of 0-30 ℃.
In the mixed reaction, the reaction temperature affects the reaction speed and the occurrence probability of side reaction between sodium alkoxide, ammonium salt and paraformaldehyde, if the reaction temperature is too low, the reaction speed is too low, the production efficiency is affected, meanwhile, the reaction cannot be fully carried out, and certain unreacted impurities exist in the mixture after the reaction; if the reaction temperature is too high, the reaction rate increases, but the occurrence probability of side reactions increases, and the yield and purity of the target product are significantly reduced.
In some embodiments, in the "mixing reaction" operation, sodium alkoxide is pre-dissolved in a first solvent to prepare a sodium alkoxide solution, and the sodium alkoxide solution is used to participate in the system reaction.
The sodium alkoxide is white powdery substance, and the sodium alkoxide solution is formed by pre-dissolving the first solvent, so that the mixing efficiency between the sodium alkoxide and the ammonium salt can be improved, and the reaction efficiency is improved.
In some embodiments, the mass concentration of sodium alkoxide in the sodium alkoxide solution is 1% -35%.
In some embodiments, the first solvent comprises one or more of methanol, ethanol, acetonitrile, chloroform, dichloromethane, ethylene glycol dimethyl ether, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, and ethyl acetate.
In some embodiments, in the "mixed reaction" operation, the paraformaldehyde is dissolved in the second solvent to prepare a paraformaldehyde solution, and the paraformaldehyde solution is used for the system reaction, or the paraformaldehyde is directly and solid put into the reaction system.
In some embodiments, the mass concentration of paraformaldehyde in the paraformaldehyde solution is 1% -20%.
In some embodiments, the second solvent comprises one or more of methanol, ethanol, acetonitrile, chloroform, dichloromethane, ethylene glycol dimethyl ether, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, and ethyl acetate.
In some embodiments, in the "mixed reaction" operation, the order of addition of materials is: the paraformaldehyde and the ammonium salt are not mixed in the absence of sodium alkoxide.
Because the reactivity between the paraformaldehyde and the ammonium salt is higher, the reaction can be carried out at normal temperature, and the mixed reaction of the paraformaldehyde and the ammonium salt has the problem of more side reactions under the condition of no sodium alkoxide, if the paraformaldehyde and the ammonium salt are mixed in advance in the operation of 'mixed reaction', the reaction can be carried out faster, and a certain amount of byproducts are generated before the sodium alkoxide is added, so that the improvement of the purity of the product is not facilitated.
In some embodiments, in the "mixed reaction" operation, the order of addition of materials is: firstly, mixing sodium alkoxide with ammonium salt, and then adding paraformaldehyde for reaction.
In some embodiments, in the "mixed reaction" operation, the order of addition of materials is: firstly, mixing sodium alkoxide with formaldehyde, and then adding ammonium salt for reaction.
In some embodiments, in the purification operation, the solvent and byproducts in the mixture are removed by distillation, so that sodium salt in the mixture is separated out to obtain a crude sodium salt product, and then the crude sodium salt product is subjected to recrystallization operation to obtain high-purity sodium salt.
Another embodiment of the present invention provides a sodium ion battery comprising a positive electrode, a negative electrode, and a sodium salt, the sodium salt being prepared by the preparation method as described above.
Due to the adoption of the preparation method, the impurity of the prepared sodium salt is reduced, and the sodium salt with higher purity is obtained, so that the standard of the battery-grade electrolyte salt is met, and the influence of the impurity in the sodium salt on the performance of the sodium ion battery is avoided.
The invention is further illustrated by the following examples.
Example 1
This example is for illustrating the preparation method of sodium salt disclosed in the present invention, comprising the following steps:
preparing 800g of dimethyl carbonate solution of 11.25% sodium methoxide, adding 112g of ammonium hexafluorophosphate at 20 ℃ and stirring and mixing uniformly, and adding 30g of paraformaldehyde solid at 20 ℃ in batches; after the addition is completed, stirring for 30min at 20 ℃; filtering to remove solid, removing solvent and byproducts by rotary evaporation to obtain crude sodium hexafluorophosphate, and dissolving and recrystallizing with dimethyl carbonate to obtain high-purity sodium hexafluorophosphate.
Examples 2 to 14
Examples 2-14 illustrate the preparation of sodium salts disclosed herein, including most of the operating steps of example 1, which differ in:
in examples 2 to 14, the ratio of paraformaldehyde, ammonium salt and sodium alkoxide, the type of ammonium salt, the reaction temperature and the feeding sequence are shown in Table 1.
Comparative examples 1 to 7
Comparative examples 1 to 7 are for comparative illustration of the preparation method of sodium salt disclosed in the present invention, comprising most of the operation steps in example 1, which are different in that:
in comparative examples 1 to 7, the ratio of paraformaldehyde, ammonium salt and sodium methoxide, the kind of ammonium salt, the reaction temperature and the feeding sequence are shown in Table 1.
Performance testing
The sodium salts prepared in examples 1 to 14 and comparative examples 1 to 7 were subjected to yield calculation and purity test, and the residual amount of ammonium ions in the sodium salts was detected, and the obtained test results were filled in table 1:
TABLE 1
As can be seen from the test results in Table 1, compared with the method for directly adopting sodium alkoxide and ammonium salt to carry out mixed reaction, in the preparation method provided by the invention, paraformaldehyde is added into a reaction system, so that the occurrence probability of side reaction can be effectively reduced, the purity of target sodium salt is improved, and the content of ammonium ions is reduced.
As can be seen from the test results of comparative example 1 and examples 11 and 12, the reaction yield and purity at 10 to 30℃are significantly higher than those at 0℃and 40℃and the reaction is presumed to be incomplete at too low a temperature, and sodium alkoxide at too high a temperature is formed by side reaction with hexafluorophosphate.
As can be seen from the test results of comparative example 1 and examples 13 and 14, the first mixing of paraformaldehyde with ammonium hexafluorophosphate significantly reduces the purity and increases the residual amount of ammonium ions.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (6)
1. A method for preparing sodium salt, which is characterized by comprising the following operation steps:
mixing reaction: pre-dissolving sodium alkoxide in a first solvent to prepare sodium alkoxide solution, taking the sodium alkoxide solution into a system reaction, and reacting sodium alkoxide, ammonium salt and paraformaldehyde, wherein the molar ratio of the sodium alkoxide to the ammonium salt to the paraformaldehyde is (3-10): (2-4): (1-3) the reaction temperature is 0-30 ℃, a mixture containing sodium salt is obtained, the sodium salt and the ammonium salt have the same anions, the anions of the ammonium salt are selected from one or more of hexafluorophosphate ions, difluorophosphate ions, monofluorophosphate ions, difluorooxalate borate ions, dioxalate borate ions and difluorosulfimide ions, and the sodium alkoxide comprises one or more of sodium methoxide, sodium ethoxide and sodium propoxide; the paraformaldehyde is selected from short-line chain polymerization state paraformaldehyde with the polymerization degree of 8-100;
the material adding sequence is as follows:
firstly, mixing sodium alkoxide with ammonium salt, and then adding paraformaldehyde for reaction;
purifying: purification from the mixture gave sodium salt.
2. The method for preparing sodium salt according to claim 1, wherein the material addition sequence is:
firstly mixing sodium methoxide with paraformaldehyde, and finally adding ammonium hexafluorophosphate.
3. The method for preparing a sodium salt according to claim 1, wherein the first solvent comprises one or more of methanol, ethanol, acetonitrile, chloroform, methylene chloride, ethylene glycol dimethyl ether, dimethyl carbonate, diethyl carbonate, methylethyl carbonate and ethyl acetate.
4. The method for preparing sodium salt according to claim 1, wherein paraformaldehyde is dissolved in the second solvent to prepare a paraformaldehyde solution, and the paraformaldehyde solution is used for the system reaction, or the paraformaldehyde is directly and solid put into the reaction system.
5. The method for preparing sodium salt according to claim 4, wherein the second solvent comprises one or more of methanol, ethanol, acetonitrile, chloroform, methylene chloride, ethylene glycol dimethyl ether, dimethyl carbonate, diethyl carbonate, methylethyl carbonate and ethyl acetate.
6. A sodium ion battery comprising a positive electrode, a negative electrode and a sodium salt, wherein the sodium salt is prepared by the preparation method according to any one of claims 1 to 5.
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| CN202311203558.5A CN116924437B (en) | 2023-09-19 | 2023-09-19 | Sodium salt preparation method and sodium ion battery |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217622A (en) * | 2017-12-21 | 2018-06-29 | 珠海市赛纬电子材料股份有限公司 | A kind of preparation method of sodium hexafluoro phosphate |
| CN114873577A (en) * | 2022-05-24 | 2022-08-09 | 江苏新泰材料科技有限公司 | Preparation method of sodium hexafluorophosphate |
| CN116715215A (en) * | 2023-08-02 | 2023-09-08 | 深圳新宙邦科技股份有限公司 | Preparation method of sodium difluorophosphate and sodium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5351463B2 (en) * | 2008-08-08 | 2013-11-27 | ステラケミファ株式会社 | Method for producing hexafluorophosphate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108217622A (en) * | 2017-12-21 | 2018-06-29 | 珠海市赛纬电子材料股份有限公司 | A kind of preparation method of sodium hexafluoro phosphate |
| CN114873577A (en) * | 2022-05-24 | 2022-08-09 | 江苏新泰材料科技有限公司 | Preparation method of sodium hexafluorophosphate |
| CN116715215A (en) * | 2023-08-02 | 2023-09-08 | 深圳新宙邦科技股份有限公司 | Preparation method of sodium difluorophosphate and sodium ion battery |
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