CN117603099A - Preparation method and application of binary fluorine-containing sulfimide alkali metal salt - Google Patents
Preparation method and application of binary fluorine-containing sulfimide alkali metal salt Download PDFInfo
- Publication number
- CN117603099A CN117603099A CN202311571649.4A CN202311571649A CN117603099A CN 117603099 A CN117603099 A CN 117603099A CN 202311571649 A CN202311571649 A CN 202311571649A CN 117603099 A CN117603099 A CN 117603099A
- Authority
- CN
- China
- Prior art keywords
- alkali metal
- fluorine
- metal salt
- binary
- dibasic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 alkali metal salt Chemical class 0.000 title claims abstract description 58
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 54
- 239000011737 fluorine Substances 0.000 title claims abstract description 54
- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- RQIMPDXRFCFBGC-UHFFFAOYSA-N n-(oxomethylidene)sulfamoyl fluoride Chemical compound FS(=O)(=O)N=C=O RQIMPDXRFCFBGC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 14
- 125000005842 heteroatom Chemical group 0.000 claims description 14
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 2
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims 2
- BUXTXUBQAKIQKS-UHFFFAOYSA-N sulfuryl diisocyanate Chemical compound O=C=NS(=O)(=O)N=C=O BUXTXUBQAKIQKS-UHFFFAOYSA-N 0.000 claims 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000011056 performance test Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- WRJWRGBVPUUDLA-UHFFFAOYSA-N chlorosulfonyl isocyanate Chemical compound ClS(=O)(=O)N=C=O WRJWRGBVPUUDLA-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 239000002001 electrolyte material Substances 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000005463 sulfonylimide group Chemical group 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- FWQVINSGEXZQHB-UHFFFAOYSA-K trifluorodysprosium Chemical compound F[Dy](F)F FWQVINSGEXZQHB-UHFFFAOYSA-K 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/34—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfuric acids
-
- 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
- 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
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a preparation method of binary fluorine-containing sulfimide alkali metal salt, which comprises the following steps: (1) Reacting fluorosulfonyl isocyanate with dibasic acid to generate a binary fluorine-containing sulfimide compound; (2) And carrying out substitution reaction on the binary fluorine-containing sulfimide compound and a metal source to obtain the binary fluorine-containing sulfimide alkali metal salt. The preparation method is simple and feasible, can effectively synthesize the binary fluorine-containing sulfimide alkali metal salt, has low cost, and can be used for large-scale industrialized mass production. The invention also provides application of the binary fluorine-containing sulfimide alkali metal salt in the electrolyte of the secondary battery, can well improve the battery performance of the secondary battery, and is favorable for popularization of the application of the binary fluorine-containing sulfimide alkali metal salt in the electrolyte and the secondary battery.
Description
Technical Field
The invention belongs to the technical field of fluorine-containing sulfonamide imine and alkali metal salts thereof, and particularly relates to a preparation method and application of a binary fluorine-containing sulfonamide imine alkali metal salt.
Background
Fluorine-containing sulfonamide imines and alkali metal salts thereof, particularly lithium and sodium salts, are important fluorine-containing organic ionic compounds. The compounds have wide application value in the fields of novel high-efficiency catalysts, secondary lithium ion (sodium ion) batteries, super capacitors, aluminum electrolytic capacitors and other clean energy devices. However, current research on fluorine-containing sulfonimide and its derivatives has focused mainly on mono-fluorine-containing sulfonimide (i.e., containing only one sulfonylimino group-SO in the molecule) 2 -N-SO 2 (-), such as perfluoroalkyl sulfonimide and its alkali metals, of which lithium bis (fluorosulfonyl) imide, lithium bis (trifluoromethylsulfonyl) imide, and the like are the most typical.
Although mono-and alkali metal salts have found widespread use in certain fields, relatively few studies have been reported with respect to di-or poly-fluoro-sulfonimides and alkali metal salts thereof. In particular, the application of binary or multi-element fluorine-containing sulfimide and alkali metal salts thereof as electrolyte materials in secondary lithium ion (sodium ion) batteries is not fully studied. Therefore, it is extremely important and promising to develop a method for preparing binary or multi-element fluorine-containing sulfimide and alkali metal salt thereof and to measure the electrochemical performance as an electrolyte material.
Disclosure of Invention
Based on the problems, the invention aims to provide a preparation method of the binary fluorine-containing sulfimide alkali metal salt, which is simple and feasible, can effectively synthesize the binary fluorine-containing sulfimide alkali metal salt, has low cost, and can be used for large-scale industrialized scale production.
In order to achieve the above object, the present invention provides a method for preparing a binary fluorine-containing sulfimide alkali metal salt, comprising the steps of:
(1) Reacting fluorosulfonyl isocyanate with dibasic acid to generate a binary fluorine-containing sulfimide compound;
(2) And carrying out substitution reaction on the binary fluorine-containing sulfimide compound and a metal source to obtain the binary fluorine-containing sulfimide alkali metal salt.
In the technical scheme of the invention, the fluoro-sulfonyl isocyanate and the dibasic acid are used as raw materials to react to prepare an intermediate product with two sulfonyl imino groups, and then the intermediate product is subjected to substitution reaction with a metal source to prepare the binary fluorine-containing sulfonyl imine alkali metal salt.
In a preferred embodiment, the mass ratio of the fluorosulfonyl isocyanate to the dibasic acid is 2-3:1.
In a preferred embodiment, the reaction temperature in step (1) is from-10℃to 45℃and the reaction time is from 6 to 24 hours.
In a preferred embodiment, the reaction temperature in step (2) is from-10℃to 45℃and the reaction time is from 3 to 24 hours.
In a preferred embodiment, the mass ratio of the binary fluorine-containing sulfimide compound to the metal source is 1:2-3.
In a preferred embodiment, the fluorosulfonyl isocyanate is obtained by fluorination of chlorosulfonyl isocyanate, which is the following reaction scheme:
in a preferred embodiment, the dibasic acid has the following formula:
wherein R is a C1-C12 hydrocarbon group, a C2-C6 cyclic hydrocarbon group, a heteroatom-containing C1-C12 hydrocarbon group or a heteroatom-containing C2-C6 cyclic hydrocarbon group.
It should be noted that the hetero atom referred to in the present invention may be, but is not limited to, oxygen, nitrogen, sulfur, etc., and the hetero atom-containing cyclic hydrocarbon group means that the cyclic hydrocarbon group contains other types of atoms such as oxygen, nitrogen, sulfur, etc., in addition to carbon and hydrogen, and these hetero atoms may be directly bonded to carbon atoms or indirectly bonded to carbon atoms. Wherein C1-C12 represents a carbon number of 1-12, and C2-C6 represents a carbon number of 2-6.
In a preferred embodiment, the binary fluorine-containing sulfimide compound has the following structural formula:
wherein R is a C1-C12 hydrocarbon group, a C2-C6 cyclic hydrocarbon group, a heteroatom-containing C1-C12 hydrocarbon group or a heteroatom-containing C2-C6 cyclic hydrocarbon group.
In a preferred embodiment, the alkali metal salt of a dibasic fluorosulfonyl imide has the formula:
wherein A is + R is a C1-C12 hydrocarbon group, a C2-C6 cyclic hydrocarbon group, a heteroatom-containing C1-C12 hydrocarbon group or a heteroatom-containing C2-C6 cyclic hydrocarbon group.
It should be noted that the reaction process of the fluorosulfonyl isocyanate and the dibasic acid is as follows:
in a preferred embodiment, the metal source is lithium hydroxide, lithium carbonate, lithium methoxide, lithium ethoxide, sodium hydroxide, sodium carbonate, sodium methoxide, or sodium ethoxide. Taking a metal source as an example, the reaction process of the binary fluorine-containing sulfimide compound and the metal source is as follows:
in a preferred embodiment, the alkali metal salt of a binary fluorosulfonyl imide is at least one of compounds 1-3:
wherein A is + Is lithium ion or sodium ion.
The invention also provides application of the binary fluorine-containing sulfimide alkali metal salt in the electrolyte of the secondary battery, and the binary fluorine-containing sulfimide alkali metal salt is prepared by the preparation method of the binary fluorine-containing sulfimide alkali metal salt, so that the binary fluorine-containing sulfimide alkali metal salt can well improve the battery performance of the secondary battery, and is beneficial to popularization of the application of the binary fluorine-containing sulfimide alkali metal salt in the electrolyte and the secondary battery.
Detailed Description
In order to further illustrate the objects, technical solutions and advantageous effects of the present invention, the present invention will be further described with reference to specific examples. The specific conditions not specified in examples and comparative examples may be carried out under the conventional conditions or the conditions recommended by the manufacturer, and the reagents or instruments used are conventional products available commercially without specifying the manufacturer.
Example 1
The preparation method of the binary fluorine-containing sulfimide alkali metal salt compound 1 comprises the following steps:
(1) 210g of dysprosium trifluoride is added into a dry 1L three-neck flask, 500g of chlorosulfonyl isocyanate is added dropwise into the flask, the reaction system is reacted for 48 hours at 70 ℃, and after the reaction is finished, the target product of fluorosulfonyl isocyanate (402 g) is distilled out at 80 ℃;
(2) Adding 20g of maleic acid into a dry 500mL three-neck flask, adding 150g of dichloromethane serving as a solvent, placing the mixture in a water bath at 0 ℃, dropwise adding 43g of fluorosulfonyl isocyanate into the mixture, enabling a reaction system to continue to react for 12h after the dropwise adding is finished, washing and cleaning the mixture with a saturated sodium chloride solution after the reaction is finished, separating the solution, drying the mixture with anhydrous magnesium sulfate, and concentrating the mixture to obtain 37g of intermediate binary fluorine-containing sulfonyl imide compounds;
(3) Adding 20g of intermediate binary fluorine-containing sulfimide compound and 3.5g of lithium hydroxide (or 5.8g of sodium hydroxide) into a dry 500ml three-neck flask, adding 100g of absolute ethyl alcohol serving as a solvent, reacting the reaction system in a water bath at 0 ℃ for 12 hours, concentrating the reaction solution after the reaction is finished, adding a recrystallization solvent methylene dichloride into the reaction solution, and filtering the reaction mixture to obtain a target product (A + 16.1g of product, A, are obtained in the case of lithium ions + 19g of the product is obtained in the case of sodium ions) as a white solid, i.e. the alkali metal salt of the binary fluorosulfonyl imide is obtained.
Examples 2 to 3
Example 2 preparation of alkali metal salt of binary fluorosulfonyl imide compound 2, example 3 preparation of alkali metal salt of binary fluorosulfonyl imide compound 3, preparation of compound 2 and compound 3 were the same as in example 1 except that different dibasic acids were used as raw materials, and that the content of fluorosulfonyl isocyanate and the content of metal source were different. The specific diacid used can be determined based on the groups corresponding to R in compound 2 and compound 3. The content of fluorosulfonyl isocyanate and metal source on the basis of the same amount of dibasic acid can be adjusted according to the molecular weight of the dibasic acid used, as exemplified by the preparation of compound 1.
The obtained compounds 1 to 3 were subjected to nuclear magnetic resonance analysis, and the results of the obtained hydrogen spectra are shown in Table 1, and it is apparent from the results of Table 1 that the compounds 1 to 3 were efficiently synthesized by the production method of the present invention.
Results of nuclear magnetic resonance hydrogen spectra of Compounds 1 to 3 (A + ＝Li + Or Na (or) + )
Application example 1
The prepared compound 1 is applied to a lithium ion battery, and specifically comprises the following steps:
1.1 preparation of electrolyte:
in a glove box (O) 2 ＜1ppm，H 2 O < 1 ppm), uniformly mixing Ethyl Propionate (EP), dimethyl carbonate (DMC) and diethyl carbonate (DEC) according to a mass ratio of 1:1:1 to obtain a mixed solvent which is used as an organic solvent, and adding a compound 1 which is used as an additive to obtain a mixed solution. Sealing and packaging the mixed solution, freezing for 2 hr in a quick freezing chamber (-4deg.C), taking out, and placing in a glove box (O) filled with nitrogen 2 ＜1ppm，H 2 O < 1 ppm), liPF is slowly added to the mixed solution 6 And (5) uniformly mixing to obtain the electrolyte.
1.2 preparation of positive plate:
ternary material LiNi 0.6 Co 0.2 Mn 0.2 Zr 0.03 O 2 Uniformly mixing a conductive agent SuperP, an adhesive PVDF and a Carbon Nano Tube (CNT) according to a mass ratio of 96.5:1.5:1:1 to prepare lithium ion battery anode slurry with certain viscosity, and coating the lithium ion battery anode slurry on an aluminum foil for a current collector, wherein the coating amount is 324g/m 2 Drying at 85 ℃ and then cold pressing; then trimming, cutting pieces, splitting, drying at 85 ℃ for 4 hours under vacuum condition after splitting, and welding the tab to prepare the lithium ion battery positive plate meeting the requirements.
1.3 preparation of a negative plate:
mixing artificial graphite and silicon according to a mass ratio of 90:10, preparing slurry with a conductive agent SuperP, a thickener CMC and an adhesive SBR (styrene butadiene rubber emulsion) according to a mass ratio of 95:1.5:1.0:2.5, uniformly mixing, coating the mixed slurry on two sides of a copper foil, drying, and rolling to obtain a negative plate, thus preparing the lithium ion battery negative plate meeting the requirements.
1.4 preparation of lithium ion batteries:
the positive plate, the negative plate and the diaphragm prepared according to the process are manufactured into a lithium ion battery with the thickness of 4.7mm, the width of 55mm and the length of 60mm through a lamination process, and the lithium ion battery is baked for 10 hours at the temperature of 75 ℃ in vacuum and injected with the electrolyte. After 24h of standing, charging to 4.45V with a constant current of 0.lC (180 mA), and then charging to a current falling to 0.05C (90 mA) with a constant voltage of 4.45V; then discharging to 3.0V at 0.2C (180 mA), repeating the charge and discharge for 2 times, and finally charging the battery to 3.8V at 0.2C (180 mA) to finish the manufacturing of the lithium ion battery.
Application examples 2 to 3
Application examples 2 to 3 differ from application example 1 in that application example 1 uses compound 1 as an additive, application example 2 uses compound 2 as an additive, application example 3 uses compound 3 as an additive, and the remainder refer to application example 1.
Each of the application examples and comparative examples was carried out in accordance with the above-described method, and the composition and content of specific electrolytes are shown in Table 2.
TABLE 2 composition and content of electrolytes of application examples and comparative examples
The lithium ion batteries prepared in each of the application examples and comparative examples were subjected to a high-temperature storage performance test, a high-temperature cycle performance test, a normal-temperature cycle performance test, and a low-temperature performance test under the following conditions, and the results are shown in table 3.
Normal temperature cycle performance test：
The lithium ion battery is charged and discharged at the normal temperature (25 ℃) at 1.0C/1.0C (the discharge capacity of the battery is C) 0 ) The upper limit voltage was 4.4V, and then charging and discharging at 1.0C/1.0C was performed for 500 weeks under normal temperature conditions (the discharge capacity of the battery was C) 1 ) The capacity retention rate was calculated.
Capacity retention= (C 1 /C 0 )*100％
High temperature cycle test：
The lithium ion battery is charged and discharged at 1.0C/1.0C once under the condition of overhigh temperature (45 ℃) (the discharge capacity of the battery is C) 0 ) The upper limit voltage was 4.4V, and then charging and discharging at 1.0C/1.0C was performed for 500 weeks under normal temperature conditions (the discharge capacity of the battery was C) 1 ) The capacity retention rate was calculated.
Capacity retention= (C 1 /C 0 )*100％
High temperature storage performance test：
Lithium ion batteries were charged and discharged at 0.3C/0.3C once (the discharge capacity of the battery was recorded as C) at normal temperature (25 ℃ C.) 0 ) Placing the battery in a 60 ℃ oven for 15d, and taking out the battery, wherein the upper limit voltage is 4.4V; the cell was placed in a 25 ℃ environment and subjected to 0.3C discharge (discharge capacity recorded as C 1 ) The method comprises the steps of carrying out a first treatment on the surface of the The lithium ion battery was then charged and discharged once at 0.3C/0.3C (the discharge capacity of the battery was recorded as C) 2 ) The capacity retention rate and the capacity recovery rate are calculated.
Capacity retention= (C 1 /C 0 )*100％
Capacity recovery rate= (C 2 /C 0 )*100％
Low temperature discharge performance test：
The lithium ion battery is charged and discharged once at 0.3C/0.3 under the condition of normal temperature (25 ℃) (the discharge capacity is C) 0 ) The upper limit voltage was 4.4V, then the battery was charged to 4.4V under a constant current and constant voltage of 0.5C, the battery was placed in an oven at-20 ℃ for 4 hours, 0.3C discharge (discharge capacity recorded as C) was performed on the battery at-20 ℃ with a cutoff voltage of 3.0V, and then the low-temperature discharge rate was calculated.
Low temperature discharge rate= (C1/C0) ×100%
Table 3 lithium ion battery performance test results
As can be seen from the data in table 3, compared with the comparative example, the application examples 1-3, in which the compounds 1-3 are added into the electrolyte respectively, significantly improve the low-temperature discharge performance, the normal-temperature cycle performance, the high-temperature cycle performance and the high-temperature storage performance of the lithium ion battery, and demonstrate that the binary fluorine-containing sulfimide alkali metal salt has a very good application prospect in the lithium ion battery.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (10)
1. A process for the preparation of a binary fluorosulfonyl imide alkali metal salt comprising the steps of:
(1) Reacting fluorosulfonyl isocyanate with dibasic acid to generate a binary fluorine-containing sulfimide compound;
(2) And carrying out substitution reaction on the binary fluorine-containing sulfimide compound and a metal source to obtain the binary fluorine-containing sulfimide alkali metal salt.
2. The method for producing a dibasic fluorine-containing sulfonimide alkali metal salt according to claim 1, wherein the mass ratio of the fluorine-containing sulfonyl isocyanate to the dibasic acid is 2 to 3:1.
3. The process for producing a dibasic fluorine-containing sulfonimide alkali metal salt according to claim 1, wherein the reaction temperature in the step (1) is-10 ℃ to 45 ℃ and the reaction time is 6 to 24 hours.
4. The method for producing a dibasic fluorine-containing sulfonimide alkali metal salt according to claim 1, wherein the mass ratio of the dibasic fluorine-containing sulfonimide compound to the metal source is 1:2-3.
5. The method for preparing the alkali metal salt of a dibasic fluorine-containing sulfimide as claimed in claim 1, wherein the structural formula of the dibasic acid is as follows:
wherein R is a C1-C12 hydrocarbon group, a C2-C6 cyclic hydrocarbon group, a heteroatom-containing C1-C12 hydrocarbon group or a heteroatom-containing C2-C6 cyclic hydrocarbon group.
6. The method for producing an alkali metal salt of a dibasic fluorine-containing sulfonimide according to claim 5, wherein the structural formula of said dibasic fluorine-containing sulfonimide compound is as follows:
wherein R is a C1-C12 hydrocarbon group, a C2-C6 cyclic hydrocarbon group, a heteroatom-containing C1-C12 hydrocarbon group or a heteroatom-containing C2-C6 cyclic hydrocarbon group.
7. The method for producing an alkali metal salt of a dibasic fluorine-containing sulfonimide according to claim 6, wherein the alkali metal salt of a dibasic fluorine-containing sulfonimide has the following structural formula:
wherein A is + Is lithium ion or sodium ion, R is C1-C12 alkyl, C2-C6 cycloalkyl, heteroatom-containing C1-C12 alkyl or heteroatom-containingC2-C6 cyclic hydrocarbon group of (C2-C6).
8. The method for producing an alkali metal salt of a binary fluorine-containing sulfonimide according to claim 7, wherein the alkali metal salt of a binary fluorine-containing sulfonimide is at least one of the compounds 1 to 3:
wherein A is + Is lithium ion or sodium ion.
9. The method for producing a binary fluorine-containing sulfimide alkali metal salt according to claim 1, wherein the metal source is lithium hydroxide, lithium carbonate, lithium methoxide, lithium ethoxide, sodium hydroxide, sodium carbonate, sodium methoxide or sodium ethoxide.
10. The use of a alkali metal salt of a binary fluorine-containing sulfonimide in an electrolyte for a secondary battery, characterized in that the alkali metal salt of a binary fluorine-containing sulfonimide is prepared by the method for preparing the alkali metal salt of a binary fluorine-containing sulfonimide according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311571649.4A CN117603099A (en) | 2023-11-23 | 2023-11-23 | Preparation method and application of binary fluorine-containing sulfimide alkali metal salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311571649.4A CN117603099A (en) | 2023-11-23 | 2023-11-23 | Preparation method and application of binary fluorine-containing sulfimide alkali metal salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117603099A true CN117603099A (en) | 2024-02-27 |
Family
ID=89949080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311571649.4A Pending CN117603099A (en) | 2023-11-23 | 2023-11-23 | Preparation method and application of binary fluorine-containing sulfimide alkali metal salt |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117603099A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118063359A (en) * | 2024-04-25 | 2024-05-24 | 蓝固(湖州)新能源科技有限公司 | Binary asymmetric organic lithium salt, electrolyte and lithium battery |
-
2023
- 2023-11-23 CN CN202311571649.4A patent/CN117603099A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118063359A (en) * | 2024-04-25 | 2024-05-24 | 蓝固(湖州)新能源科技有限公司 | Binary asymmetric organic lithium salt, electrolyte and lithium battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2003536229A (en) | Electrolyte salt for lithium battery | |
| JP6170646B1 (en) | Electrolyte composition, secondary battery, and method of using secondary battery | |
| CN117603099A (en) | Preparation method and application of binary fluorine-containing sulfimide alkali metal salt | |
| CN111934015B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery containing non-aqueous electrolyte | |
| KR20170037977A (en) | Fluorinated carbonates comprising two oxygen bearing functional groups | |
| CN110343125B (en) | Method for preparing high-purity proportional mixed lithium salt at low cost and application of mixed lithium salt in lithium ion battery | |
| EP3373379A1 (en) | Additive for nonaqueous electrolyte solutions, nonaqueous electrolyte solution and electricity storage device | |
| CN108997217B (en) | Difluorophosphoric acid imidazole ionic liquid, preparation method thereof, electrolyte and application | |
| CN117049486A (en) | Preparation method of sodium bis (fluorosulfonyl) imide | |
| CN110627742B (en) | Preparation method and purification method of compound containing at least one cyclic ligand structure | |
| CN113549047A (en) | Preparation method of fluoro alkyl sultone | |
| CN113416178B (en) | Lithium battery additive amido vinyl sulfate, and preparation method and application thereof | |
| CN112358465B (en) | Compound, electrolyte composed of compound and lithium ion battery | |
| CN114649582A (en) | Electrolyte containing six-membered cyclic nitrogen-based salt structure and preparation method and application thereof | |
| CN116621739A (en) | Preparation method of binary fluorine-containing sulfimide alkali metal salt and application of alkali metal salt | |
| CN111883835B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery | |
| CN114649577A (en) | Sulfur-based saturated carbon chain electrolyte and preparation method and application thereof | |
| CN118221712A (en) | Lithium borate containing dimercapto and preparation method thereof | |
| CN117682487A (en) | Preparation method of fluorine-containing lithium sulfonyl imide, nonaqueous electrolyte and lithium ion battery | |
| CN114649578A (en) | Saturated heterochain sulfur-based electrolyte and preparation method and application thereof | |
| CN114230587A (en) | Electrolyte containing saturated heterocycles and preparation and application thereof | |
| CN115197259A (en) | Unsaturated bond-containing organic alkali metal trifluoroborate salt and preparation method and application thereof | |
| CN117551055A (en) | Electrolyte additive, preparation method thereof, nonaqueous electrolyte and alkali metal battery | |
| CN116936909A (en) | High-voltage electrolyte for lithium battery | |
| CN116445941A (en) | Preparation method of fluorine-containing sulfonate, electrolyte and electrochemical device thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |