CN114552019A - Complex anion sodium salt and preparation method and use method thereof - Google Patents
Complex anion sodium salt and preparation method and use method thereof Download PDFInfo
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- CN114552019A CN114552019A CN202210272612.0A CN202210272612A CN114552019A CN 114552019 A CN114552019 A CN 114552019A CN 202210272612 A CN202210272612 A CN 202210272612A CN 114552019 A CN114552019 A CN 114552019A
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- -1 anion sodium salt Chemical class 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 56
- 239000002904 solvent Substances 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 26
- 150000001450 anions Chemical class 0.000 claims abstract description 23
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 23
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 14
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 11
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000003446 ligand Substances 0.000 claims abstract description 5
- 150000001768 cations Chemical class 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 26
- 239000011734 sodium Substances 0.000 claims description 23
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052708 sodium Inorganic materials 0.000 claims description 12
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 10
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 7
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 7
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 6
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 claims description 5
- 229910016913 AlY3 Inorganic materials 0.000 claims description 4
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 229940021013 electrolyte solution Drugs 0.000 description 21
- 238000001291 vacuum drying Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000005456 alcohol based solvent Substances 0.000 description 3
- 239000003495 polar organic solvent Substances 0.000 description 2
- 150000005838 radical anions Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SFEBPWPPVGRFOA-UHFFFAOYSA-N trifluoromethanesulfinic acid Chemical compound OS(=O)C(F)(F)F SFEBPWPPVGRFOA-UHFFFAOYSA-N 0.000 description 2
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/20—Thiocyanic acid; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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 complex anion sodium salt and a preparation method and a using method thereof. The core cation of the complex anion is an aluminum ion, the ligand is an anion capable of forming a coordination compound with the aluminum ion, and the coordination number is between 4 and 6. The preparation method of the complex anion sodium salt comprises the steps of respectively preparing aluminum trichloride and alcohol-soluble sodium salt into solutions according to stoichiometric ratio, quickly mixing the solutions, removing precipitates, and evaporating the solvent to obtain the target compound. The complex anion sodium salt is dissolved in a carbonate solvent, and the electrolyte solution of the secondary sodium-ion battery can be used.
Description
Technical Field
The invention belongs to the field of energy sources, and particularly relates to a sodium ion electrolyte based on complex anions and a preparation method and a use method thereof.
Background
The lithium ion batteries used in large quantities at present have potential safety hazards such as resource shortage, too fast rising of raw material cost, spontaneous combustion risk and the like. Compared with the lithium ion battery, the sodium ion battery has rich raw material sources, and the safety performance and the cost performance are superior to those of the lithium ion battery. The main obstacle in the development and application of sodium ion batteries is the electrolyte solution matched with the anode material. Compared with the similar lithium ion compounds, the solubility of sodium ion salts in carbonate solvents is low, and if other organic solvents are used for preparing sodium ion electrolyte solutions, the problems of compatibility, matching, safety, environmental friendliness and the like with solution electrode materials exist, so that the practical application of sodium ion batteries is limited.
Disclosure of Invention
The invention aims to provide a targeted solution for the bottleneck technology of a sodium ion battery, namely a complex anion sodium salt, a preparation method and a use method thereof, and aims to promote the practical application of the sodium ion battery.
In order to achieve the purpose of the invention, the specific technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a complex anion sodium salt having the formula Nax[AlY3+x]Wherein Al is used as the core cation of the complex anion, Y is used as the anion of the ligand acid radical, and x is 1 to 3.
As a preferred aspect of the above first aspect, the coordinator anion is an anion capable of forming a coordination compound with an aluminum ion, including but not limited to trifluoroacetate, trifluoromethanesulfonate, trifluoromethylsulfinate, hexafluorophosphate or thiocyanate.
In a second aspect, the present invention provides a process for the preparation of a complex anion sodium salt, comprising the steps of:
1) respectively dissolving aluminum trichloride and a sodium source compound with the molar ratio of 1 (3+ x) by using an alcohol solvent to obtain a solution A and a solution B, wherein anions of the sodium source compound can form a coordination compound with aluminum ions;
2) rapidly mixing the solution A and the solution B while stirring, continuously stirring until the precipitation is complete, and separating the precipitation to obtain a clear solution;
3) stirring, heating and evaporating the solvent to obtain the target compound complex anion sodium salt.
In the second aspect, the alcohol solvent is preferably methanol or ethanol.
Preferably, in the second aspect, the method for separating the precipitate is suction filtration, filtration or centrifugation.
As a preferred aspect of the second aspect, the sodium source compound is an alcohol-soluble sodium salt, including but not limited to sodium trifluoroacetate, sodium trifluoromethanesulfonate, sodium hexafluorophosphate, sodium thiocyanate.
In the second aspect, the solvent is preferably evaporated by stirring and heating under vacuum, and the heating temperature is preferably not higher than the decomposition temperature of the complex anion sodium salt.
In a third aspect, the present invention provides a complex anion sodium salt prepared by the preparation method according to any one of the second aspect.
In a fourth aspect, the present invention provides a method of using a complex anion sodium salt according to any of the first or third aspects above, by: and dissolving the complex anion sodium salt in a carbonate solvent to prepare a solution with the concentration of 10-30%, and filling the solution into a secondary sodium-ion battery to be used as a sodium-ion electrolyte solution.
As a preferred aspect of the fourth aspect, the carbonate compound includes, but is not limited to, one or more of γ -butyrolactone, propylene carbonate, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate.
The solubility and the conductivity of the complex anion sodium salt provided by the invention in a carbonate solvent are higher than those of common organic acid and inorganic acid sodium salts, and the complex anion sodium salt is suitable for preparing an electrolyte solution of a secondary sodium-ion battery. The complex anion sodium salt has simple preparation technology, is easy to realize industrialization, can effectively reduce the cost of the sodium ion battery, and promotes the practical application of the sodium ion battery.
Detailed Description
The invention will be further illustrated and described with reference to specific embodiments. The technical features of the various implementations may be combined without conflict with each other and do not constitute a limitation to the present invention.
In a first aspect, the invention provides a complex anion sodium salt of formula Nax[AlY3+x]Wherein Al is the core cation of complex anion, Y is the anion of ligand acid radical, and x is 1-3. The ligand is an anion capable of forming a complex with aluminium ions, the coordination number of which is between 4 and 6 according to the above formula.
In the present invention, the coordinator anion in the sodium salt of the complex anion is an anion capable of forming a coordination compound with aluminum ions, and includes, but is not limited to, trifluoroacetate, trifluoromethanesulfonate, trifluoromethylsulfinate, hexafluorophosphate and thiocyanate.
The complex formed by combining the aluminum ions and the acid radical anions is stable in chemical property in a polar organic solvent and has higher solubility and conductivity. The complex anion sodium salt of the present invention is more suitable for use as a sodium ion battery electrolyte solution than conventional sodium salts.
In a second aspect, the present invention provides a process for the preparation of the complex anion sodium salt, which comprises the steps of:
1) adding aluminum trichloride and a sodium source compound in a molar ratio of 1 (3+ x) into two containers respectively, wherein the amounts of the aluminum trichloride and the sodium source compound are consistent with the molecular formula Nax[AlY3+x]The solution A and the solution B are obtained after the given stoichiometric ratio is respectively dissolved by using an alcohol solvent.
The sodium source compound in the invention is an alcohol-soluble sodium salt, and the anion of the sodium source compound can form a coordination compound with aluminum ions, including but not limited to sodium trifluoroacetate, sodium trifluoromethanesulfonate, sodium hexafluorophosphate and sodium thiocyanate.
Aluminum trichloride and the alcohol-soluble sodium source compound are both easily soluble in alcohol solvents, so methanol or ethanol can be used as a reaction medium, and the alcohol solvents can also adopt mixtures or other feasible alcohol solvents besides methanol or ethanol.
2) Rapidly mixing the solution A and the solution B while stirring, continuously stirring until the precipitate is complete, and filtering or centrifuging to remove the precipitate to obtain a clear solution.
The two solutions are mixed immediately before precipitation reaction occurs, namely: chloride ions from solution a and sodium ions from solution B combine to form a precipitate of NaCl that is insoluble in alcohol. Taking sodium thiocyanate NaSCN as an example, the reaction formula is as follows:
AlCl3+3NaSCN＝Al(SCN)3+3NaCl↓ (1)
after the reaction of the formula (1), the formed NaCl precipitate can be separated by conventional technical means such as suction filtration, centrifugation and the like, sodium salt (x is 1 to 3) with the molar number x times of aluminum ions still remains in the clear liquid after separation and precipitation, and the remaining sodium salt and the aluminum ions can further react to generate complex anion sodium salt, wherein the reaction formula is as follows:
Al(SCN)3+xNaSCN＝Nax[Al(SCN)3+x] (2)
thiocyanate in the formulas (1) and (2) can be replaced by other acid radical anions capable of forming a complex with aluminum ions, such as trifluoroacetate, trifluoromethanesulfonate and hexafluorophosphate, so that sodium trifluoroacetate, sodium trifluoromethanesulfonate and sodium hexafluorophosphate can be used as the corresponding sodium source compound to replace NaSCN in the formulas.
3) Stirring, heating and evaporating the solvent to obtain the target compound complex anion sodium salt.
The technique used to evaporate the solvent is conventional, but care should be taken that the heating temperature does not exceed the decomposition temperature of the complex anion sodium salt. It is recommended to evaporate the solvent using vacuum drying techniques to avoid thermal decomposition and oxidation of the product.
In a third aspect of the present invention, there is provided a use method of the complex anion sodium salt, specifically: the complex anion sodium salt is dissolved in a carbonate solvent to prepare a solution with the concentration of 10-30%, and then the solution is filled in a secondary sodium ion battery to be used as a sodium ion electrolyte solution.
The carbonate compound in the invention includes but is not limited to one or more of gamma-butyrolactone, propylene carbonate, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.
The carbonate compound as a polar organic solvent has stable chemical properties, does not react with complex anion sodium salt in an electrolyte solution, and has no corrosion to the anode and the cathode of the battery. The carbonate solvents are usually mixed for use so as to adjust the properties of the electrolyte solution, such as viscosity, dielectric constant, melting point, boiling point and the like, and adapt to different use environments and working conditions. The specific proportion can refer to the existing lithium ion electrolyte solution formula. After the solution is prepared, the solution is stored in a sealed way to prevent moisture absorption; before use, the battery needs to be heated and dehumidified to prevent the electrode of the battery from reacting with water.
The complex anion sodium salt-carbonate solution provided by the invention is suitable for being used as electrolyte solutions of various types of secondary sodium-ion batteries.
The present invention will be described in detail with reference to examples, in which examples 1 to 5 describe specific implementations of a method for preparing a complex anion sodium salt, and examples 6 to 10 describe specific implementations of a method for preparing an electrolyte solution for a secondary sodium ion battery using the prepared complex anion sodium salt.
Example 1
The preparation method of the complex anion sodium salt comprises the following specific steps:
1) 133.34 g (1 mol) of aluminum trichloride and 486.42 g (6 mol) of sodium thiocyanate were added into two containers, and dissolved in ethanol to obtain a solution A and a solution B.
2) Rapidly mixing the solution A and the solution B while stirring, continuously stirring until the precipitate is complete, and filtering or centrifuging to remove the precipitate to obtain a clear solution.
3) Stirring, heating and evaporating solvent ethanol by vacuum drying technology to obtain target compound Na3[Al(SCN)6]。
Example 2
The preparation method of the complex anion sodium salt comprises the following specific steps:
1) 133.34 g (1 mol) of aluminum trichloride and 671.8 g (4 mol) of sodium hexafluorophosphate were added to each vessel and dissolved in methanol to obtain solution A and solution B, respectively.
2) Rapidly mixing the solution A and the solution B while stirring, continuously stirring until the precipitate is complete, and filtering or centrifuging to remove the precipitate to obtain a clear solution.
3) Stirring, heating and evaporating the solvent methanol by a vacuum drying technology to obtain a target compound Na [ Al (PF)6)4]。
Example 3
The preparation method of the complex anion sodium salt comprises the following specific steps:
1) 133.34 g (1 mol) of aluminum trichloride and 780.3 g (5 mol) of sodium trifluoromethanesulfonate were added to two containers, and dissolved in methanol and ethanol, respectively, to obtain a solution A and a solution B.
2) Rapidly mixing the solution A and the solution B while stirring, continuously stirring until the precipitate is complete, and filtering or centrifuging to remove the precipitate to obtain a clear solution.
3) Stirring, heating and evaporating the solvents methanol and ethanol by a vacuum drying technology to obtain the target compound Na2[Al(CO2F3S)5]。
Example 4
The preparation method of the complex anion sodium salt comprises the following specific steps:
1) 133.34 g (1 mol) of aluminum trichloride and 688.23 g (4 mol) of sodium trifluoromethanesulfonate were added to two containers, and dissolved in methanol to obtain a solution A and a solution B, respectively.
2) Rapidly mixing the solution A and the solution B while stirring, continuously stirring until the precipitate is complete, and filtering or centrifuging to remove the precipitate to obtain a clear solution.
3) Stirring, heating and evaporating the solvent methanol by a vacuum drying technology to obtain a target compound Na [ Al (CO)3F3S)4]。
Example 5
The preparation method of the complex anion sodium salt comprises the following specific steps:
1) 133.34 g (1 mol) of aluminum trichloride and 680.05 g (5 mol) of sodium trifluoroacetate were added to two containers, and dissolved in ethanol to obtain a solution A and a solution B.
2) Rapidly mixing the solution A and the solution B while stirring, continuously stirring until the precipitate is complete, and filtering or centrifuging to remove the precipitate to obtain a clear solution.
3) Stirring, heating and evaporating solvent ethanol by vacuum drying technology to obtain target compound Na2[Al(C2O2F3)5]。
Example 6
In this example, an electrolyte solution of complex anion sodium salt is prepared, and the specific process is as follows:
1) ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and dimethyl carbonate (DMC) were mixed in a weight ratio of 4:2:4 to obtain a mixed carbonate solvent.
2) 30 g of complex anion sodium salt Na3[Al(SCN)6]Dissolved in 70 g of a mixed carbonate solvent to obtain a 30% sodium ion electrolyte solution.
Example 7
In this example, an electrolyte solution of complex anion sodium salt is prepared, and the specific process is as follows:
1) ethylene Carbonate (EC), Ethyl Methyl Carbonate (EMC) and Propylene Carbonate (PC) were mixed in a weight ratio of 4:2:4 to obtain a mixed carbonate solvent.
2) 10 g of complex anion sodium salt Na [ Al (PF)6)4]Dissolved in 90 g of mixed carbonate solvent to obtain a 10% sodium ion electrolyte solution.
Example 8
In this example, an electrolyte solution of complex anion sodium salt is prepared, and the specific process is as follows:
1) ethylene Carbonate (EC), gamma-butyrolactone (GBL) and Propylene Carbonate (PC) were mixed in a weight ratio of 4:2:4 to obtain a mixed carbonate solvent.
2) 20 g of complex anion sodium salt Na2[Al(CO2F3S)5]Dissolved in 80 g of mixed carbonate solvent to obtain a sodium ion electrolyte solution with the concentration of 20%.
Example 9
In this example, an electrolyte solution of complex anion sodium salt is prepared, and the specific process is as follows:
1) ethylene Carbonate (EC), γ -butyrolactone (GBL) and diethyl carbonate (DEC) were mixed in a weight ratio of 4:2:4 to obtain a mixed carbonate solvent.
2) 20 g of the complex anion sodium salt Na [ Al (CO)3F3S)4]Dissolved in 80 g of a mixed carbonate solvent to obtain a sodium ion electrolyte solution having a concentration of 20%.
Example 10
In this example, an electrolyte solution of complex anion sodium salt is prepared, and the specific process is as follows:
1) ethylene Carbonate (EC) and Propylene Carbonate (PC) were mixed in a weight ratio of 1:1 to obtain a mixed carbonate solvent.
2) 30 g of complex anion sodium salt Na2[Al(C2O2F3)5]Dissolved in 70 g of a mixed carbonate solvent to obtain a 30% sodium ion electrolyte solution.
The above-described embodiments are merely preferred embodiments of the present invention, which should not be construed as limiting the invention. Various changes and modifications may be made by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present invention. Therefore, the technical scheme obtained by adopting the mode of equivalent replacement or equivalent transformation is within the protection scope of the invention.
Claims (10)
1. A complex anion sodium salt with the molecular formula of Nax[AlY3+x]Wherein Al is used as the core cation of the complex anion, Y is used as the anion of the ligand acid radical, and x is 1 to 3.
2. A complex anion, sodium salt, according to claim 1, characterised in that the coordinator anion is an anion capable of forming a coordination compound with aluminium ions, including but not limited to trifluoroacetate, triflate, hexafluorophosphate or thiocyanate.
3. A preparation method of complex anion sodium salt is characterized by comprising the following steps:
1) respectively dissolving aluminum trichloride and a sodium source compound with the molar ratio of 1 (3+ x) by using an alcohol solvent to obtain a solution A and a solution B, wherein anions of the sodium source compound can form a coordination compound with aluminum ions;
2) rapidly mixing the solution A and the solution B while stirring, continuously stirring until the precipitation is complete, and separating the precipitation to obtain a clear solution;
3) stirring, heating and evaporating the solvent to obtain the target compound complex anion sodium salt.
4. The method according to claim 3, wherein the alcoholic solvent is methanol or ethanol.
5. The method according to claim 3, wherein the method for separating the precipitate is suction filtration, filtration or centrifugation.
6. The method of claim 3, wherein the sodium source compound is an alcohol soluble sodium salt including but not limited to sodium trifluoroacetate, sodium trifluoromethanesulfonate, sodium hexafluorophosphate, sodium thiocyanate.
7. The method according to claim 3, wherein the solvent is evaporated by heating while stirring at a temperature not higher than the decomposition temperature of the complex anion sodium salt under vacuum.
8. A complex anion sodium salt prepared by the preparation method according to any one of claims 3 to 7.
9. A method for using the complex anion sodium salt according to claim 1 or 8, wherein the complex anion sodium salt is dissolved in a carbonate solvent to prepare a solution having a concentration of 10% to 30%, and the solution is poured into a secondary sodium ion battery and used as a sodium ion electrolyte solution.
10. The use of claim 9, wherein the carbonate based compound comprises one or more of but not limited to γ -butyrolactone, propylene carbonate, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate.
Priority Applications (1)
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