CN117682487A - Preparation method of fluorine-containing lithium sulfonyl imide, nonaqueous electrolyte and lithium ion battery - Google Patents
Preparation method of fluorine-containing lithium sulfonyl imide, nonaqueous electrolyte and lithium ion battery Download PDFInfo
- Publication number
- CN117682487A CN117682487A CN202311710236.XA CN202311710236A CN117682487A CN 117682487 A CN117682487 A CN 117682487A CN 202311710236 A CN202311710236 A CN 202311710236A CN 117682487 A CN117682487 A CN 117682487A
- Authority
- CN
- China
- Prior art keywords
- lithium
- fluorine
- electrolytic solution
- nonaqueous
- carbonate
- 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
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 46
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 43
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000011737 fluorine Substances 0.000 title claims abstract description 42
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 29
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 20
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical compound CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 claims abstract description 10
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims abstract description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 14
- 229910003002 lithium salt Inorganic materials 0.000 claims description 14
- 159000000002 lithium salts Chemical class 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 10
- 239000008151 electrolyte solution Substances 0.000 claims description 10
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 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 8
- 239000002904 solvent Substances 0.000 claims description 7
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 description 18
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 229940125904 compound 1 Drugs 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000006256 anode slurry Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013716 LiNi Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000000806 fluorine-19 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000003839 salts Chemical class 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
- 239000002562 thickening agent Substances 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
- Secondary Cells (AREA)
Abstract
The invention provides a preparation method of fluorine-containing lithium sulfonyl imide, a nonaqueous electrolyte and a lithium ion battery. The preparation method of the fluorine-containing lithium sulfonyl imide comprises the following steps: s1, reacting methylsulfonamide and sulfonyl chloride under certain conditions to obtain an intermediate; s2, reacting the intermediate with lithium fluoride under a certain condition to obtain fluorine-containing lithium sulfonyl imide shown in a formula I; the fluorine-containing lithium sulfonyl imide prepared by the method is applied to the non-aqueous electrolyte, so that the corrosion of an aluminum current collector can be slowed down, and the cycle life of the lithium ion battery can be ensured under the condition of high-rate charge and discharge.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a preparation method of fluorine-containing lithium sulfonyl imide, a nonaqueous electrolyte and a lithium ion battery.
Background
With the expansion of new energy automobile markets, people put forward higher requirements on the charging speed of new energy automobiles, so that new energy automobile enterprises are promoted to have higher requirements on the charging speed of lithium ion batteries, and the existing LiPF (lithium ion power filter) 6 The electrolyte cannot meet the requirement of high-rate charging of the battery, liFSI has better high-rate charging performance, but LiFSI has quite large problems, one of the problems is that LiFSI can dissolve an aluminum current collector, so that a positive electrode is corroded, and finally the service life of the lithium ion battery is reduced.
Therefore, it is important to develop an electrolyte salt capable of improving high-rate charge and discharge of a battery and having a long life.
Disclosure of Invention
The invention aims to provide a preparation method of fluorine-containing lithium sulfonyl imide, which can effectively relieve corrosion of an aluminum current collector and further ensure multiplying power performance and cycle performance of a lithium ion battery by applying the fluorine-containing lithium sulfonyl imide prepared by the method to non-aqueous electrolyte.
In order to achieve the above object, the first aspect of the present invention provides a method for preparing fluorine-containing lithium sulfonyl imide, comprising the steps of:
s1, reacting methylsulfonamide and sulfonyl chloride under certain conditions to obtain an intermediate;
s2, reacting the intermediate with lithium fluoride under a certain condition to obtain fluorine-containing lithium sulfonyl imide shown in a formula I;
compared with the prior art, the preparation method is simple and easy to implement, and the prepared fluorine-containing lithium sulfonyl imide can be applied to the nonaqueous electrolyte to effectively relieve corrosion of an aluminum current collector so as to ensure the multiplying power performance and the cycle performance of the lithium ion battery. Compared with the lithium bis (fluorosulfonyl) imide in the prior art, the lithium bis (fluorosulfonyl) imide disclosed by the invention only contains one fluorine atom, and the other fluorine atom is substituted by methyl, so that the electronegativity of one part of the lithium bis (fluorosulfonyl) imide is reduced, and the lithium bis (fluorosulfonyl) imide disclosed by the invention does not have the capability of dissolving aluminum foil, but has the high rate performance of the lithium bis (fluorosulfonyl) imide, so that the cycle performance of a lithium ion battery can be ensured under the condition of high-rate charge and discharge when the lithium bis (fluorosulfonyl) imide is applied to a nonaqueous electrolyte.
Preferably, in S1, the molar ratio of the methylsulfonamide to the sulfonyl chloride is 1:2-2:1, and the certain condition comprises the reaction for 6-12 h at 95-150 ℃; in S2, the molar ratio of the intermediate to the lithium fluoride is 1:2-2:1, and the certain condition comprises the reaction for 4-8 h at 45-85 ℃.
In order to achieve the above object, a second aspect of the present invention provides a nonaqueous electrolytic solution comprising a lithium salt and a nonaqueous solvent, the lithium salt comprising a fluorine-containing sulfonimide lithium prepared by the above-described preparation method.
Preferably, the mass percentage of the fluorine-containing sulfimide lithium in the nonaqueous electrolyte is 0.1-15%, and the fluorine-containing sulfimide lithium can be independently used as lithium salt to be applied to the nonaqueous electrolyte, and can also be used as an additive to be matched with other lithium salts to be applied to the nonaqueous electrolyte.
Preferably, the lithium salt further comprises at least one of lithium hexafluorophosphate and lithium bis-fluorosulfonyl imide.
Preferably, the method comprises the steps of. The mass percentage of the lithium salt in the nonaqueous electrolyte is 0.5-15%.
Preferably, the nonaqueous electrolytic solution of the present invention further comprises an auxiliary agent comprising one or more of Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PST) and vinyl sulfate (DTD).
Preferably, the mass percentage of the auxiliary agent in the nonaqueous electrolyte is 0.1% -5%.
Preferably, the nonaqueous solvent includes at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), ethylene Carbonate (EC), propylene Carbonate (PC), ethyl Acetate (EA), propyl acetate (n-PA), ethyl Propionate (EP), and propyl propionate (n-PP).
The third aspect of the invention provides a lithium ion battery comprising the non-aqueous electrolyte.
Drawings
FIG. 1 is a 1H NMR spectrum of a lithium fluorosulfonyl imide of the present invention;
FIG. 2 is a 19F NMR spectrum of a lithium fluorosulfonyl imide of the present invention.
Detailed Description
The lithium ion battery comprises a nonaqueous electrolyte, a positive electrode and a negative electrode. The positive electrode comprises a positive electrode material, and the positive electrode material is lithium iron phosphate or lithium nickel cobalt manganate. The negative electrode comprises a negative electrode material, and the negative electrode material is a silicon-carbon negative electrode material. The nonaqueous electrolyte comprises a lithium salt, a nonaqueous solvent and an auxiliary agent, wherein the lithium salt at least comprises fluorine-containing lithium sulfonyl imide. The lithium salt may also include lithium hexafluorophosphate (LiPF) 6 ) And at least one of lithium bis (fluorosulfonyl) imide (LiFSI), wherein the mass percentage of lithium salt in the nonaqueous electrolyte is 0.5% -15%, and particularly but not limited to 0.5%, 1%, 2%, 5%, 10%, 12%, 15%. The nonaqueous solvent includes at least one of dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), ethylene Carbonate (EC), propylene Carbonate (PC), ethyl Acetate (EA), propyl acetate (n-PA), ethyl Propionate (EP), and propyl propionate (n-PP). The auxiliary agent comprisesThe mass percentage of the auxiliary agent in the nonaqueous electrolyte is 0.1% -5%, specifically but not limited to 0.1%, 0.2%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% and 5.0%. The mass percentage of the fluorine-containing lithium sulfonyl imide in the nonaqueous electrolyte is 0.1% -15%, and the specific mass percentage is not limited to 0.1%, 0.5%, 1.0%, 2.0%, 4.0%, 6.0%, 8.0%, 10..0%, 12.0%, 14.0% and 15.0%, and the structure of the fluorine-containing lithium sulfonyl imide is shown as formula one:
the preparation method of the fluorine-containing lithium sulfonyl imide comprises the following steps:
s1 methylsulfonamide and sulfonyl chloride react for 6h to 12h at the temperature of 95 ℃ to 150 ℃ to obtain an intermediate, wherein the molar ratio of the methylsulfonamide to the sulfonyl chloride is 1:2 to 2:1, specifically but not limited to 1.0:2.0, 1.0:1.8, 1.0:1.6, 1.0:1.4, 1.0:1.2, 1.0:1.0, 1.2:1.0, 1.4:1.0, 1.6:1.0, 1.8:1.0 and 2.0:1.0, and preferably 1.0:1.0. The reaction temperature is particularly but not limited to 95 ℃,100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, preferably 125 ℃. The reaction time is particularly but not limited to 6h, 7h, 8h, 9h, 10h, 11h, 12h, preferably 8h.
S2, reacting the intermediate and lithium fluoride for 4-8 hours at 45-85 ℃ to obtain fluorine-containing lithium sulfonyl imide, wherein the molar ratio of the intermediate to the lithium fluoride is 1:2-2:1, specifically but not limited to 1.0:2.0, 1.0:1.8, 1.0:1.6, 1.0:1.4, 1.0:1.2, 1.0:1.0, 1.2:1.0, 1.4:1.0, 1.6:1.0, 1.8:1.0, 2.0:1.0, and preferably 1.0:1.0. The reaction temperature is specifically but not limited to 45 ℃,50 ℃, 55 ℃, 60 ℃,65 ℃, 70 ℃, 75 ℃,80 ℃, 85 ℃, preferably 65 ℃. The reaction time is particularly but not limited to 4h, 5h, 6h, 7h, 8h, preferably 6h.
For a better description of the objects, technical solutions and advantageous effects of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention and should not be taken as limiting the present invention.
Example 1
The embodiment provides a preparation method of fluorine-containing lithium sulfonyl imide, which comprises the following steps:
s1 into a 0.5L three-necked flask filled with nitrogen atmosphere, 95.1g (1.0 mol) of methylsulfonamide and 135.0g (1.0 mol) of sulfonyl chloride were added, the mixture was stirred at 125℃for reaction for 8 hours, by-product hydrogen chloride was removed by vacuum concentration at 45℃and vacuum distillation was carried out to obtain 165.1g of an intermediate, the yield was 85.3%.1H NMR (60 MHz, DMSO): delta 2.97; delta 6.78. The preparation route is as follows:
s2 into a 2L three-neck flask filled with nitrogen atmosphere, 26g (1.0 mol) of lithium fluoride and 732.0g of dimethyl carbonate are added, stirring is carried out at 65 ℃ for reaction, 193.6g (1.0 mol) of intermediate is gradually added dropwise, reaction is carried out for 6 hours after the dropwise addition is completed, by-product hydrogen chloride is removed by vacuum concentration at 45 ℃, filtration is carried out, dimethyl carbonate is removed by vacuum concentration, dichloromethane crystallization is added, and vacuum drying at 95 ℃ is carried out, thus 154.1g of fluorine-containing sulfimide compound which is marked as compound 1, the yield is 84.2%, the purity is 99.5%, the moisture is 85ppm, and the acid value is 78ppm.1H NMR (60 MHz, DMSO): δ2.84. 19F NMR (60 MHz): delta 62.25. The specific spectrograms are shown in fig. 1 and 2, and the specific preparation route is as follows:
example 2
The embodiment provides a preparation method of fluorine-containing lithium sulfonyl imide, which comprises the following steps:
s1 into a 0.5L three-necked flask filled with nitrogen atmosphere, 190.2g (2.0 mol) of methylsulfonamide and 135.0g (1.0 mol) of sulfonyl chloride were added, the mixture was stirred at 100℃for reaction for 11 hours, by-product hydrogen chloride was removed by vacuum concentration at 45℃and vacuum distillation was carried out to obtain 127.4g of an intermediate, the yield was 65.8%.
S2 into a 2L three-neck flask filled with nitrogen atmosphere, 52.0g (2.0 mol) of lithium fluoride and 732.0g of dimethyl carbonate are added, stirring is carried out at 50 ℃ for reaction, 193.6g (1.0 mol) of intermediate is gradually added dropwise, reaction is carried out for 8 hours after the dropwise addition is completed, by-product hydrogen chloride is removed by vacuum concentration at 45 ℃, filtration is carried out, dimethyl carbonate is removed by vacuum concentration, dichloromethane crystallization is added, 95 ℃ vacuum drying is carried out, 103.9g of fluorine-containing sulfimide compound is obtained, and the obtained product is marked as compound 1, the yield is 56.8%, the purity is 99.5%, the moisture is 85ppm, and the acid value is 78ppm.
Example 3
The embodiment provides a preparation method of fluorine-containing lithium sulfonyl imide, which comprises the following steps:
s1 into a 0.5L three-necked flask filled with nitrogen atmosphere, 95.1g (1.0 mol) of methylsulfonamide and 270.0g (2.0 mol) of sulfonyl chloride were added, the mixture was stirred and reacted at 145℃for 5 hours, by-product hydrogen chloride was removed by vacuum concentration at 45℃and vacuum distillation was carried out to obtain 145.7g of an intermediate, the yield was 75.3%.
S2 in a 2L three-neck flask filled with nitrogen atmosphere, 26g (1.0 mol) of lithium fluoride and 732.0g of dimethyl carbonate are added, stirring is carried out at 80 ℃ for reaction, 387.2g (2.0 mol) of intermediate is gradually added dropwise, reaction is carried out for 4.5 hours after the dropwise addition is completed, by-product hydrogen chloride is removed by vacuum concentration at 45 ℃, filtration is carried out, dimethyl carbonate is removed by vacuum concentration, dichloromethane crystallization is added, 95 ℃ vacuum drying is carried out, 106.3g of fluorine-containing sulfimide compound is obtained, and the obtained product is marked as compound 1, the yield is 58.1%, the purity is 99.5%, the moisture is 85ppm, and the acid value is 78ppm.
The fluorine-containing lithium sulfonyl imide (compound 1) prepared in the example 1 is applied to a nonaqueous electrolyte of a lithium ion battery, and specifically comprises the following steps:
experiment one
(1) Arrangement of electrolyte
In a glove box with water content less than 1ppm, oxygen content less than 1ppm and nitrogen purity more than 99.9999%, uniformly mixing Ethylene Carbonate (EC) and dimethyl carbonate (DMC) according to a mass ratio of 1:2.32 to obtain 87.0g of mixed solvent as an organic solvent, adding 13g of fluorine-containing lithium sulfonyl imide (compound 1), and uniformly mixing to obtain the electrolyte.
(2) Preparation of positive plate
Ternary material LiNi 0.8 Co 0.1 Mn 0.1 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.
(3) Preparing 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
(4) Preparation of a lithium ion battery:
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.
(5) High rate cycle performance test
The capacity retention rate was calculated by charging and discharging the lithium ion battery once at 4.0C/4.0C at normal temperature with an upper limit voltage of 4.2V, and then charging and discharging at 4.0C/4.0C for 500 weeks:
capacity retention= (battery capacity C after 500 weeks of cycle 1 Initial capacity C of battery 0 )*100%。
The composition, content and capacity retention results of the electrolytes of experiments one to fourteen and comparative experiments one to three are shown in table 1, wherein the preparation process and high-rate cycle performance test conditions and methods of the lithium ion battery electrolytes, the positive electrode sheet, the negative electrode sheet and the lithium ion battery of experiments two to fourteen and comparative experiments one to three are the same as those of example 1.
TABLE 1
As can be seen from the capacity retention test data of the cycle performance at the high rate in table 1, the test results from experiment one to experiment fourteen are superior to those from experiment one to experiment fourteen, probably because the nonaqueous electrolyte from experiment one to experiment fourteen contains the fluorine-containing lithium sulfonimide according to the invention, and compared with the fluorine-containing lithium sulfonimide in the prior art, the fluorine-containing lithium sulfonimide according to the invention contains only one fluorine atom, and the other fluorine atom is substituted by methyl, so that the electronegativity of a part of the fluorine-containing lithium sulfonimide is reduced, and the fluorine-containing lithium sulfonimide does not have the capability of dissolving aluminum foil, but has the high rate performance of the fluorine-containing lithium sulfonimide in the prior art, so that the cycle performance of the lithium ion battery can be ensured under the condition of high rate charge and discharge when the fluorine-containing lithium imide lithium ion battery is applied to the nonaqueous electrolyte. The specific analysis in combination with the experimental examples and the comparative examples is as follows:
as shown by the experimental comparison results of the experiment I, the experiment II and the experiment III, the performance of the fluorine-containing lithium sulfonyl imide (compound 1) is better when the mass percentage of the fluorine-containing lithium sulfonyl imide in the electrolyte is 13 percent;
as can be seen from the comparison results of experiments one, four and five, when the nonaqueous solvent is a mixed solvent composed of ethylene carbonate and dimethyl carbonate, and the mass ratio of the ethylene carbonate to the dimethyl carbonate (EC): the non-aqueous electrolyte performance of the dimethyl carbonate (DMC) is better when the DMC is 1:2.32;
from the experimental comparison results of experiments one, six, seven and eight and the experimental comparison results of experiments eleven, twelve, thirteen and fourteen, the nonaqueous electrolyte solution using the fluorine-containing lithium sulfonyl imide (compound 1) alone has better performance;
according to experimental comparison results of experiments one, nine, ten and eleven, the performance of the compound 1 is obviously improved by adding the auxiliary agent on the basis of the compound; when a mixing aid is used, the performance is more excellent.
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. The preparation method of the fluorine-containing lithium sulfonyl imide is characterized by comprising the following steps:
s1, reacting methylsulfonamide and sulfonyl chloride under certain conditions to obtain an intermediate;
s2, reacting the intermediate with lithium fluoride under a certain condition to obtain fluorine-containing lithium sulfonyl imide shown in a formula I;
2. the nonaqueous electrolytic solution according to claim 1, wherein in S1, a molar ratio of the methylsulfonamide to the sulfonyl chloride is 1:2 to 2:1, and the certain condition includes a reaction at 95 ℃ to 150 ℃ for 6 hours to 12 hours; in S2, the molar ratio of the intermediate to the lithium fluoride is 1:2-2:1, and the certain condition comprises the reaction for 4-8 h at 45-85 ℃.
3. A nonaqueous electrolyte comprising a lithium salt and a nonaqueous solvent, wherein the lithium salt comprises the fluorine-containing lithium sulfonyl imide prepared by the preparation method according to any one of claims 1 to 2.
4. The nonaqueous electrolytic solution according to claim 3, wherein the mass percentage of the fluorine-containing lithium sulfonimide in the nonaqueous electrolytic solution is 0.1% to 15%.
5. The nonaqueous electrolytic solution according to claim 3, wherein the lithium salt further comprises at least one of lithium hexafluorophosphate and lithium difluorosulfonimide.
6. The nonaqueous electrolytic solution according to claim 3, wherein the mass percentage of the lithium salt in the nonaqueous electrolytic solution is 0.5% to 15%.
7. The nonaqueous electrolyte of claim 3, further comprising an auxiliary agent comprising one or more of vinylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone and vinyl sulfate.
8. The nonaqueous electrolytic solution according to claim 3, wherein the mass percentage of the auxiliary agent in the nonaqueous electrolytic solution is 0.1% to 5%.
9. The nonaqueous electrolyte according to claim 3, wherein the nonaqueous solvent comprises at least one of dimethyl carbonate, diethyl carbonate, methylethyl carbonate, ethylene carbonate, propylene carbonate, ethyl acetate, propyl acetate, ethyl propionate, and propyl propionate.
10. A lithium ion battery comprising the nonaqueous electrolyte according to any one of claims 3 to 9.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311710236.XA CN117682487A (en) | 2023-12-12 | 2023-12-12 | Preparation method of fluorine-containing lithium sulfonyl imide, nonaqueous electrolyte and lithium ion battery |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202311710236.XA CN117682487A (en) | 2023-12-12 | 2023-12-12 | Preparation method of fluorine-containing lithium sulfonyl imide, nonaqueous electrolyte and lithium ion battery |
Publications (1)
Publication Number | Publication Date |
---|---|
CN117682487A true CN117682487A (en) | 2024-03-12 |
Family
ID=90129725
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202311710236.XA Pending CN117682487A (en) | 2023-12-12 | 2023-12-12 | Preparation method of fluorine-containing lithium sulfonyl imide, nonaqueous electrolyte and lithium ion battery |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN117682487A (en) |
-
2023
- 2023-12-12 CN CN202311710236.XA patent/CN117682487A/en active Pending
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP2023043812A (en) | Non-aqueous electrolyte for lithium ion battery and use thereof | |
CN110931865A (en) | Novel additive-containing electrolyte for lithium ion battery and lithium ion battery | |
CN111934015B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery containing non-aqueous electrolyte | |
CN110911748B (en) | Lithium secondary battery electrolyte and lithium secondary battery | |
WO2023040119A1 (en) | Electrolyte additive, electrolyte containing same, and lithium-ion battery | |
CN110416611B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same | |
CN113113668B (en) | Electrolyte additive, non-aqueous electrolyte containing electrolyte additive and lithium ion battery | |
CN111477961B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery containing non-aqueous electrolyte | |
CN111370764B (en) | Non-aqueous electrolyte and lithium ion battery containing same | |
CN117304098A (en) | Electrolyte additive, preparation method thereof, electrolyte and lithium ion battery | |
CN109818062B (en) | Ternary lithium ion battery and electrolyte thereof | |
CN113871712B (en) | Lithium ion battery electrolyte, preparation method thereof and lithium ion battery | |
CN110247116B (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery using same | |
CN114883648A (en) | Non-aqueous electrolyte of lithium ion battery and lithium ion battery | |
CN117682487A (en) | Preparation method of fluorine-containing lithium sulfonyl imide, nonaqueous electrolyte and lithium ion battery | |
CN108400382A (en) | Electrolyte solution and secondary battery | |
CN114695960A (en) | Novel additive with high and low temperature performance, preparation method and application thereof | |
CN113517471B (en) | Non-aqueous electrolyte of lithium ion battery and application thereof | |
CN113651839B (en) | Electrolyte additive for improving high and low temperature performance of lithium battery, preparation method thereof, electrolyte and electrochemical device | |
CN117039160A (en) | Electrolyte and lithium ion battery using same | |
CN114649577A (en) | Sulfur-based saturated carbon chain electrolyte and preparation method and application thereof | |
CN114621264A (en) | Electrolyte containing saturated carbon chain structure and preparation method and application thereof | |
CN115732756A (en) | Electrolyte and secondary battery using same | |
CN118156606A (en) | Electrolyte, electrochemical device comprising same and vehicle | |
EP4113689A1 (en) | Electrolytic solution for secondary battery and lithium secondary battery including the same |
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 |